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Dr. Laurie Starkey

Dr. Laurie Starkey

Biomolecules

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Table of Contents

I. Introduction to Organic Molecules
Introduction and Drawing Structures

49m 51s

Intro
0:00
Organic Chemistry
0:07
Organic
0:08
Inorganic
0:26
Examples of Organic Compounds
1:16
Review Some Chemistry Basics
5:23
Electrons
5:42
Orbitals (s,p,d,f)
6:12
Review Some Chemistry Basics
7:35
Elements & Noble Gases
7:36
Atom & Valance Shell
8:47
Review Some Chemistry Basics
11:33
Electronegative Elements
11:34
Which Is More Electronegative, C or N?
13:45
Ionic & Covalent Bonds
14:07
Ionic Bonds
14:08
Covalent Bonds
16:17
Polar Covalent Bonds
19:35
Polar Covalent Bonds & Electronegativities
19:37
Polarity of Molecules
22:56
Linear molecule
23:07
Bent Molecule
23:53
No Polar Bonds
24:21
Ionic
24:52
Line Drawings
26:36
Line Drawing Overview
26:37
Line Drawing: Example 1
27:12
Line Drawing: Example 2
29:14
Line Drawing: Example 3
29:51
Line Drawing: Example 4
30:34
Line Drawing: Example 5
31:21
Line Drawing: Example 6
32:41
Diversity of Organic Compounds
33:57
Diversity of Organic Compounds
33:58
Diversity of Organic Compounds, cont.
39:16
Diversity of Organic Compounds, cont.
39:17
Examples of Polymers
45:26
Examples of Polymers
45:27
Lewis Structures & Resonance

44m 25s

Intro
0:00
Lewis Structures
0:08
How to Draw a Lewis Structure
0:09
Examples
2:20
Lewis Structures
6:25
Examples: Lewis Structure
6:27
Determining Formal Charges
8:48
Example: Determining Formal Charges for Carbon
10:11
Example: Determining Formal Charges for Oxygen
11:02
Lewis Structures
12:08
Typical, Stable Bonding Patterns: Hydrogen
12:11
Typical, Stable Bonding Patterns: Carbon
12:58
Typical, Stable Bonding Patterns: Nitrogen
13:25
Typical, Stable Bonding Patterns: Oxygen
13:54
Typical, Stable Bonding Patterns: Halogen
14:16
Lewis Structure Example
15:17
Drawing a Lewis Structure for Nitric Acid
15:18
Resonance
21:58
Definition of Resonance
22:00
Delocalization
22:07
Hybrid Structure
22:38
Rules for Estimating Stability of Resonance Structures
26:04
Rule Number 1: Complete Octets
26:10
Rule Number 2: Separation of Charge
28:13
Rule Number 3: Negative and Positive Charges
30:02
Rule Number 4: Equivalent
31:06
Looking for Resonance
32:09
Lone Pair Next to a p Bond
32:10
Vacancy Next to a p Bond
33:53
p Bond Between Two Different Elements
35:00
Other Type of Resonance: Benzene
36:06
Resonance Example
37:29
Draw and Rank Resonance Forms
37:30
Acid-Base Reactions

1h 7m 46s

Intro
0:00
Acid-Base Reactions
0:07
Overview
0:08
Lewis Acid and Lewis Base
0:30
Example 1: Lewis Acid and Lewis Base
1:53
Example 2: Lewis Acid and Lewis Base
3:04
Acid-base Reactions
4:54
Bonsted-Lowry Acid and Bonsted-Lowry Base
4:56
Proton Transfer Reaction
5:36
Acid-Base Equilibrium
8:14
Two Acids in Competition = Equilibrium
8:15
Example: Which is the Stronger Acid?
8:40
Periodic Trends for Acidity
12:40
Across Row
12:41
Periodic Trends for Acidity
19:48
Energy Diagram
19:50
Periodic Trends for Acidity
21:28
Down a Family
21:29
Inductive Effects on Acidity
25:52
Example: Which is the Stronger Acid?
25:54
Other Electron-Withdrawing Group (EWG)
30:37
Inductive Effects on Acidity
32:55
Inductive Effects Decrease with Distance
32:56
Resonance Effects on Acidity
36:35
Examples of Resonance Effects on Acidity
36:36
Resonance Effects on Acidity
41:15
Small and Large Amount of Resonance
41:17
Acid-Base Example
43:10
Which is Most Acidic? Which is the Least Acidic?
43:12
Acid-Base Example
49:26
Which is the Stronger Base?
49:27
Acid-Base Example
53:58
Which is the Strongest Base?
53:59
Common Acids/Bases
1:00:45
Common Acids/Bases
1:00:46
Example: Determine the Direction of Equilibrium
1:04:51
Structures and Properties of Organic Molecules

1h 23m 35s

Intro
0:00
Orbitals and Bonding
0:20
Atomic Orbitals (AO)
0:21
Molecular Orbitals (MO)
1:46
Definition of Molecular Orbitals
1:47
Example 1: Formation of Sigma Bond and Molecular Orbitals
2:20
Molecular Orbitals (MO)
5:25
Example 2: Formation of Pi Bond
5:26
Overlapping E Levels of MO's
7:28
Energy Diagram
7:29
Electronic Transitions
9:18
Electronic Transitions
9:23
Hybrid Orbitals
12:04
Carbon AO
12:06
Hybridization
13:51
Hybrid Orbitals
15:02
Examples of Hybrid Orbitals
15:05
Example: Assign Hybridization
20:31
3-D Sketches
24:05
sp3
24:24
sp2
25:28
sp
27:41
3-D Sketches of Molecules
29:07
3-D Sketches of Molecules 1
29:08
3-D Sketches of Molecules 2
32:29
3-D Sketches of Molecules 3
35:36
3D Sketch
37:20
How to Draw 3D Sketch
37:22
Example 1: Drawing 3D Sketch
37:50
Example 2: Drawing 3D Sketch
43:04
Hybridization and Resonance
46:06
Example: Hybridization and Resonance
46:08
Physical Properties
49:55
Water Solubility, Boiling Points, and Intermolecular Forces
49:56
Types of 'Nonbonding' Interactions
51:47
Dipole-Dipole
52:37
Definition of Dipole-Dipole
52:39
Example: Dipole-Dipole Bonding
53:27
Hydrogen Bonding
57:14
Definition of Hydrogen Bonding
57:15
Example: Hydrogen Bonding
58:05
Van Der Waals/ London Forces
1:03:11
Van Der Waals/ London Forces
1:03:12
Example: Van Der Waals/ London Forces
1:04:59
Water Solubility
1:08:32
Water Solubility
1:08:34
Example: Water Solubility
1:09:05
Example: Acetone
1:11:29
Isomerism
1:13:51
Definition of Isomers
1:13:53
Constitutional Isomers and Example
1:14:17
Stereoisomers and Example
1:15:34
Introduction to Functional Groups
1:17:06
Functional Groups: Example, Abbreviation, and Name
1:17:07
Introduction to Functional Groups
1:20:48
Functional Groups: Example, Abbreviation, and Name
1:20:49
Alkane Structures

1h 13m 38s

Intro
0:00
Nomenclature of Alkanes
0:12
Nomenclature of Alkanes and IUPAC Rules
0:13
Examples: Nomenclature of Alkanes
4:38
Molecular Formula and Degrees of Unsaturation (DU)
17:24
Alkane Formula
17:25
Example: Heptane
17:58
Why '2n+2' Hydrogens?
18:35
Adding a Ring
19:20
Adding a p Bond
19:42
Example 1: Determine Degrees of Unsaturation (DU)
20:17
Example 2: Determine Degrees of Unsaturation (DU)
21:35
Example 3: Determine DU of Benzene
23:30
Molecular Formula and Degrees of Unsaturation (DU)
24:41
Example 4: Draw Isomers
24:42
Physical properties of Alkanes
29:17
Physical properties of Alkanes
29:18
Conformations of Alkanes
33:40
Conformational Isomers
33:42
Conformations of Ethane: Eclipsed and Staggered
34:40
Newman Projection of Ethane
36:15
Conformations of Ethane
40:38
Energy and Degrees Rotated Diagram
40:41
Conformations of Butane
42:28
Butane
42:29
Newman Projection of Butane
43:35
Conformations of Butane
44:25
Energy and Degrees Rotated Diagram
44:30
Cycloalkanes
51:26
Cyclopropane and Cyclobutane
51:27
Cyclopentane
53:56
Cycloalkanes
54:56
Cyclohexane: Chair, Boat, and Twist Boat Conformations
54:57
Drawing a Cyclohexane Chair
57:58
Drawing a Cyclohexane Chair
57:59
Newman Projection of Cyclohexane
1:02:14
Cyclohexane Chair Flips
1:04:06
Axial and Equatorial Groups
1:04:10
Example: Chair Flip on Methylcyclohexane
1:06:44
Cyclohexane Conformations Example
1:09:01
Chair Conformations of cis-1-t-butyl-4-methylcyclohexane
1:09:02
Stereochemistry

1h 40m 54s

Intro
0:00
Stereochemistry
0:10
Isomers
0:11
Stereoisomer Examples
1:30
Alkenes
1:31
Cycloalkanes
2:35
Stereoisomer Examples
4:00
Tetrahedral Carbon: Superimposable (Identical)
4:01
Tetrahedral Carbon: Non-Superimposable (Stereoisomers)
5:18
Chirality
7:18
Stereoisomers
7:19
Chiral
8:05
Achiral
8:29
Example: Achiral and Chiral
8:45
Chirality
20:11
Superimposable, Non-Superimposable, Chiral, and Achiral
20:12
Nomenclature
23:00
Cahn-Ingold-Prelog Rules
23:01
Nomenclature
29:39
Example 1: Nomenclature
29:40
Example 2: Nomenclature
31:49
Example 3: Nomenclature
33:24
Example 4: Nomenclature
35:39
Drawing Stereoisomers
36:58
Drawing (S)-2-bromopentane
36:59
Drawing the Enantiomer of (S)-2-bromopentane: Method 1
38:47
Drawing the Enantiomer of (S)-2-bromopentane: Method 2
39:35
Fischer Projections
41:47
Definition of Fischer Projections
41:49
Drawing Fischer Projection
43:43
Use of Fisher Projection: Assigning Configuration
49:13
Molecules with Two Chiral Carbons
51:49
Example A
51:42
Drawing Enantiomer of Example A
53:26
Fischer Projection of A
54:25
Drawing Stereoisomers, cont.
59:40
Drawing Stereoisomers Examples
59:41
Diastereomers
1:01:48
Drawing Stereoisomers
1:06:37
Draw All Stereoisomers of 2,3-dichlorobutane
1:06:38
Molecules with Two Chiral Centers
1:10:22
Draw All Stereoisomers of 2,3-dichlorobutane, cont.
1:10:23
Optical Activity
1:14:10
Chiral Molecules
1:14:11
Angle of Rotation
1:14:51
Achiral Species
1:16:46
Physical Properties of Stereoisomers
1:17:11
Enantiomers
1:17:12
Diastereomers
1:18:01
Example
1:18:26
Physical Properties of Stereoisomers
1:23:05
When Do Enantiomers Behave Differently?
1:23:06
Racemic Mixtures
1:28:18
Racemic Mixtures
1:28:21
Resolution
1:29:52
Unequal Mixtures of Enantiomers
1:32:54
Enantiomeric Excess (ee)
1:32:55
Unequal Mixture of Enantiomers
1:34:43
Unequal Mixture of Enantiomers
1:34:44
Example: Finding ee
1:36:38
Example: Percent of Composition
1:39:46
II. Understanding Organic Reactions
Nomenclature

1h 53m 47s

Intro
0:00
Cycloalkane Nomenclature
0:17
Cycloalkane Nomenclature and Examples
0:18
Alkene Nomenclature
6:28
Alkene Nomenclature and Examples
6:29
Alkene Nomenclature: Stereochemistry
15:07
Alkenes With Two Groups: Cis & Trans
15:08
Alkenes With Greater Than Two Groups: E & Z
18:26
Alkyne Nomenclature
24:46
Alkyne Nomenclature and Examples
24:47
Alkane Has a Higher Priority Than Alkyne
28:25
Alcohol Nomenclature
29:24
Alcohol Nomenclature and Examples
29:25
Alcohol FG Has Priority Over Alkene/yne
33:41
Ether Nomenclature
36:32
Ether Nomenclature and Examples
36:33
Amine Nomenclature
42:59
Amine Nomenclature and Examples
43:00
Amine Nomenclature
49:45
Primary, Secondary, Tertiary, Quaternary Salt
49:46
Aldehyde Nomenclature
51:37
Aldehyde Nomenclature and Examples
51:38
Ketone Nomenclature
58:43
Ketone Nomenclature and Examples
58:44
Aromatic Nomenclature
1:05:02
Aromatic Nomenclature and Examples
1:05:03
Aromatic Nomenclature, cont.
1:09:09
Ortho, Meta, and Para
1:09:10
Aromatic Nomenclature, cont.
1:13:27
Common Names for Simple Substituted Aromatic Compounds
1:13:28
Carboxylic Acid Nomenclature
1:16:35
Carboxylic Acid Nomenclature and Examples
1:16:36
Carboxylic Acid Derivatives
1:22:28
Carboxylic Acid Derivatives
1:22:42
General Structure
1:23:10
Acid Halide Nomenclature
1:24:48
Acid Halide Nomenclature and Examples
1:24:49
Anhydride Nomenclature
1:28:10
Anhydride Nomenclature and Examples
1:28:11
Ester Nomenclature
1:32:50
Ester Nomenclature
1:32:51
Carboxylate Salts
1:38:51
Amide Nomenclature
1:40:02
Amide Nomenclature and Examples
1:40:03
Nitrile Nomenclature
1:45:22
Nitrile Nomenclature and Examples
1:45:23
Chemical Reactions

51m 1s

Intro
0:00
Chemical Reactions
0:06
Reactants and Products
0:07
Thermodynamics
0:50
Equilibrium Constant
1:06
Equation
2:35
Organic Reaction
3:05
Energy vs. Progress of Rxn Diagrams
3:48
Exothermic Reaction
4:02
Endothermic Reaction
6:54
Estimating ΔH rxn
9:15
Bond Breaking
10:03
Bond Formation
10:25
Bond Strength
11:35
Homolytic Cleavage
11:59
Bond Dissociation Energy (BDE) Table
12:29
BDE for Multiple Bonds
14:32
Examples
17:35
Kinetics
20:35
Kinetics
20:36
Examples
21:49
Reaction Rate Variables
23:15
Reaction Rate Variables
23:16
Increasing Temperature, Increasing Rate
24:08
Increasing Concentration, Increasing Rate
25:39
Decreasing Energy of Activation, Increasing Rate
27:49
Two-Step Mechanisms
30:06
E vs. POR Diagram (2-step Mechanism)
30:07
Reactive Intermediates
33:03
Reactive Intermediates
33:04
Example: A Carbocation
35:20
Carbocation Stability
37:24
Relative Stability of Carbocation
37:25
Alkyl groups and Hyperconjugation
38:45
Carbocation Stability
41:57
Carbocation Stabilized by Resonance: Allylic
41:58
Carbocation Stabilized by Resonance: Benzylic
42:59
Overall Carbocation Stability
44:05
Free Radicals
45:05
Definition and Examples of Free Radicals
45:06
Radical Mechanisms
49:40
Example: Regular Arrow
49:41
Example: Fish-Hook Arrow
50:17
Free Radical Halogenation

26m 23s

Intro
0:00
Free Radical Halogenation
0:06
Free Radical Halogenation
0:07
Mechanism: Initiation
1:27
Mechanism: Propagation Steps
2:21
Free Radical Halogenation
5:33
Termination Steps
5:36
Example 1: Terminations Steps
6:00
Example 2: Terminations Steps
6:18
Example 3: Terminations Steps
7:43
Example 4: Terminations Steps
8:04
Regiochemistry of Free Radical Halogenation
9:32
Which Site/Region Reacts and Why?
9:34
Bromination and Rate of Reaction
14:03
Regiochemistry of Free Radical Halogenation
14:30
Chlorination
14:31
Why the Difference in Selectivity?
19:58
Allylic Halogenation
20:53
Examples of Allylic Halogenation
20:55
Substitution Reactions

1h 48m 5s

Intro
0:00
Substitution Reactions
0:06
Substitution Reactions Example
0:07
Nucleophile
0:39
Electrophile
1:20
Leaving Group
2:56
General Reaction
4:13
Substitution Reactions
4:43
General Reaction
4:46
Substitution Reaction Mechanisms: Simultaneous
5:08
Substitution Reaction Mechanisms: Stepwise
5:34
SN2 Substitution
6:21
Example of SN2 Mechanism
6:22
SN2 Kinetics
7:58
Rate of SN2
9:10
Sterics Affect Rate of SN2
9:12
Rate of SN2 (By Type of RX)
14:13
SN2: E vs. POR Diagram
17:26
E vs. POR Diagram
17:27
Transition State (TS)
18:24
SN2 Transition State, Kinetics
20:58
SN2 Transition State, Kinetics
20:59
Hybridization of TS Carbon
21:57
Example: Allylic LG
23:34
Stereochemistry of SN2
25:46
Backside Attack and Inversion of Stereochemistry
25:48
SN2 Summary
29:56
Summary of SN2
29:58
Predict Products (SN2)
31:42
Example 1: Predict Products
31:50
Example 2: Predict Products
33:38
Example 3: Predict Products
35:11
Example 4: Predict Products
36:11
Example 5: Predict Products
37:32
SN1 Substitution Mechanism
41:52
Is This Substitution? Could This Be an SN2 Mechanism?
41:54
SN1 Mechanism
43:50
Two Key Steps: 1. Loss of LG
43:53
Two Key Steps: 2. Addition of nu
45:11
SN1 Kinetics
47:17
Kinetics of SN1
47:18
Rate of SN1 (By RX type)
48:44
SN1 E vs. POR Diagram
49:49
E vs. POR Diagram
49:51
First Transition Stage (TS-1)
51:48
Second Transition Stage (TS-2)
52:56
Stereochemistry of SN1
53:44
Racemization of SN1 and Achiral Carbocation Intermediate
53:46
Example
54:29
SN1 Summary
58:25
Summary of SN1
58:26
SN1 or SN2 Mechanisms?
1:00:40
Example 1: SN1 or SN2 Mechanisms
1:00:42
Example 2: SN1 or SN2 Mechanisms
1:03:00
Example 3: SN1 or SN2 Mechanisms
1:04:06
Example 4: SN1 or SN2 Mechanisms
1:06:17
SN1 Mechanism
1:09:12
Three Steps of SN1 Mechanism
1:09:13
SN1 Carbocation Rearrangements
1:14:50
Carbocation Rearrangements Example
1:14:51
SN1 Carbocation Rearrangements
1:20:46
Alkyl Groups Can Also Shift
1:20:48
Leaving Groups
1:24:26
Leaving Groups
1:24:27
Forward or Reverse Reaction Favored?
1:26:00
Leaving Groups
1:29:59
Making poor LG Better: Method 1
1:30:00
Leaving Groups
1:34:18
Making poor LG Better: Tosylate (Method 2)
1:34:19
Synthesis Problem
1:38:15
Example: Provide the Necessary Reagents
1:38:16
Nucleophilicity
1:41:10
What Makes a Good Nucleophile?
1:41:11
Nucleophilicity
1:44:45
Periodic Trends: Across Row
1:44:47
Periodic Trends: Down a Family
1:46:46
Elimination Reactions

1h 11m 43s

Intro
0:00
Elimination Reactions: E2 Mechanism
0:06
E2 Mechanism
0:08
Example of E2 Mechanism
1:01
Stereochemistry of E2
4:48
Anti-Coplanar & Anti-Elimination
4:50
Example 1: Stereochemistry of E2
5:34
Example 2: Stereochemistry of E2
10:39
Regiochemistry of E2
13:04
Refiochemistry of E2 and Zaitsev's Rule
13:05
Alkene Stability
17:39
Alkene Stability
19:20
Alkene Stability Examples
19:22
Example 1: Draw Both E2 Products and Select Major
21:57
Example 2: Draw Both E2 Products and Select Major
25:02
SN2 Vs. E2 Mechanisms
29:06
SN2 Vs. E2 Mechanisms
29:07
When Do They Compete?
30:34
SN2 Vs. E2 Mechanisms
31:23
Compare Rates
31:24
SN2 Vs. E2 Mechanisms
36:34
t-BuBr: What If Vary Base?
36:35
Preference for E2 Over SN2 (By RX Type)
40:42
E1 Elimination Mechanism
41:51
E1 - Elimination Unimolecular
41:52
E1 Mechanism: Step 1
44:14
E1 Mechanism: Step 2
44:48
E1 Kinetics
46:58
Rate = k[RCI]
47:00
E1 Rate (By Type of Carbon Bearing LG)
48:31
E1 Stereochemistry
49:49
Example 1: E1 Stereochemistry
49:51
Example 2: E1 Stereochemistry
52:31
Carbocation Rearrangements
55:57
Carbocation Rearrangements
56:01
Product Mixtures
57:20
Predict the Product: SN2 vs. E2
59:58
Example 1: Predict the Product
1:00:00
Example 2: Predict the Product
1:02:10
Example 3: Predict the Product
1:04:07
Predict the Product: SN2 vs. E2
1:06:06
Example 4: Predict the Product
1:06:07
Example 5: Predict the Product
1:07:29
Example 6: Predict the Product
1:07:51
Example 7: Predict the Product
1:09:18
III. Alkanes, Alkenes, & Alkynes
Alkenes

36m 39s

Intro
0:00
Alkenes
0:12
Definition and Structure of Alkenes
0:13
3D Sketch of Alkenes
1:53
Pi Bonds
3:48
Alkene Stability
4:57
Alkyl Groups Attached
4:58
Trans & Cis
6:20
Alkene Stability
8:42
Pi Bonds & Conjugation
8:43
Bridgehead Carbons & Bredt's Rule
10:22
Measuring Stability: Hydrogenation Reaction
11:40
Alkene Synthesis
12:01
Method 1: E2 on Alkyl Halides
12:02
Review: Stereochemistry
16:17
Review: Regiochemistry
16:50
Review: SN2 vs. E2
17:34
Alkene Synthesis
18:57
Method 2: Dehydration of Alcohols
18:58
Mechanism
20:08
Alkene Synthesis
23:26
Alcohol Dehydration
23:27
Example 1: Comparing Strong Acids
26:59
Example 2: Mechanism for Dehydration Reaction
29:00
Example 3: Transform
32:50
Reactions of Alkenes

2h 8m 44s

Intro
0:00
Reactions of Alkenes
0:05
Electrophilic Addition Reaction
0:06
Addition of HX
2:02
Example: Regioselectivity & 2 Steps Mechanism
2:03
Markovnikov Addition
5:30
Markovnikov Addition is Favored
5:31
Graph: E vs. POR
6:33
Example
8:29
Example: Predict and Consider the Stereochemistry
8:30
Hydration of Alkenes
12:31
Acid-catalyzed Addition of Water
12:32
Strong Acid
14:20
Hydration of Alkenes
15:20
Acid-catalyzed Addition of Water: Mechanism
15:21
Hydration vs. Dehydration
19:51
Hydration Mechanism is Exact Reverse of Dehydration
19:52
Example
21:28
Example: Hydration Reaction
21:29
Alternative 'Hydration' Methods
25:26
Oxymercuration-Demercuration
25:27
Oxymercuration Mechanism
28:55
Mechanism of Oxymercuration
28:56
Alternative 'Hydration' Methods
30:51
Hydroboration-Oxidation
30:52
Hydroboration Mechanism
33:22
1-step (concerted)
33:23
Regioselective
34:45
Stereoselective
35:30
Example
35:58
Example: Hydroboration-Oxidation
35:59
Example
40:42
Example: Predict the Major Product
40:43
Synthetic Utility of 'Alternate' Hydration Methods
44:36
Example: Synthetic Utility of 'Alternate' Hydration Methods
44:37
Flashcards
47:28
Tips On Using Flashcards
47:29
Bromination of Alkenes
49:51
Anti-Addition of Br₂
49:52
Bromination Mechanism
53:16
Mechanism of Bromination
53:17
Bromination Mechanism
55:42
Mechanism of Bromination
55:43
Bromination: Halohydrin Formation
58:54
Addition of other Nu: to Bromonium Ion
58:55
Mechanism
1:00:08
Halohydrin: Regiochemistry
1:03:55
Halohydrin: Regiochemistry
1:03:56
Bromonium Ion Intermediate
1:04:26
Example
1:09:28
Example: Predict Major Product
1:09:29
Example Cont.
1:10:59
Example: Predict Major Product Cont.
1:11:00
Catalytic Hydrogenation of Alkenes
1:13:19
Features of Catalytic Hydrogenation
1:13:20
Catalytic Hydrogenation of Alkenes
1:14:48
Metal Surface
1:14:49
Heterogeneous Catalysts
1:15:29
Homogeneous Catalysts
1:16:08
Catalytic Hydrogenation of Alkenes
1:17:44
Hydrogenation & Pi Bond Stability
1:17:45
Energy Diagram
1:19:22
Catalytic Hydrogenation of Dienes
1:20:40
Hydrogenation & Pi Bond Stability
1:20:41
Energy Diagram
1:23:31
Example
1:24:14
Example: Predict Product
1:24:15
Oxidation of Alkenes
1:27:21
Redox Review
1:27:22
Epoxide
1:30:26
Diol (Glycol)
1:30:54
Ketone/ Aldehyde
1:31:13
Epoxidation
1:32:08
Epoxidation
1:32:09
General Mechanism
1:36:32
Alternate Epoxide Synthesis
1:37:38
Alternate Epoxide Synthesis
1:37:39
Dihydroxylation
1:41:10
Dihydroxylation
1:41:12
General Mechanism (Concerted Via Cycle Intermediate)
1:42:38
Ozonolysis
1:44:22
Ozonolysis: Introduction
1:44:23
Ozonolysis: Is It Good or Bad?
1:45:05
Ozonolysis Reaction
1:48:54
Examples
1:51:10
Example 1: Ozonolysis
1:51:11
Example
1:53:25
Radical Addition to Alkenes
1:55:05
Recall: Free-Radical Halogenation
1:55:15
Radical Mechanism
1:55:45
Propagation Steps
1:58:01
Atom Abstraction
1:58:30
Addition to Alkene
1:59:11
Radical Addition to Alkenes
1:59:54
Markovnivok (Electrophilic Addition) & anti-Mark. (Radical Addition)
1:59:55
Mechanism
2:01:03
Alkene Polymerization
2:05:35
Example: Alkene Polymerization
2:05:36
Alkynes

1h 13m 19s

Intro
0:00
Structure of Alkynes
0:04
Structure of Alkynes
0:05
3D Sketch
2:30
Internal and Terminal
4:03
Reductions of Alkynes
4:36
Catalytic Hydrogenation
4:37
Lindlar Catalyst
5:25
Reductions of Alkynes
7:24
Dissolving Metal Reduction
7:25
Oxidation of Alkynes
9:24
Ozonolysis
9:25
Reactions of Alkynes
10:56
Addition Reactions: Bromination
10:57
Addition of HX
12:24
Addition of HX
12:25
Addition of HX
13:36
Addition of HX: Mechanism
13:37
Example
17:38
Example: Transform
17:39
Hydration of Alkynes
23:35
Hydration of Alkynes
23:36
Hydration of Alkynes
26:47
Hydration of Alkynes: Mechanism
26:49
'Hydration' via Hydroboration-Oxidation
32:57
'Hydration' via Hydroboration-Oxidation
32:58
Disiamylborane
33:28
Hydroboration-Oxidation Cont.
34:25
Alkyne Synthesis
36:17
Method 1: Alkyne Synthesis By Dehydrohalogenation
36:19
Alkyne Synthesis
39:06
Example: Transform
39:07
Alkyne Synthesis
41:21
Method 2 & Acidity of Alkynes
41:22
Conjugate Bases
43:06
Preparation of Acetylide Anions
49:55
Preparation of Acetylide Anions
49:57
Alkyne Synthesis
53:40
Synthesis Using Acetylide Anions
53:41
Example 1: Transform
57:04
Example 2: Transform
1:01:07
Example 3: Transform
1:06:22
IV. Alcohols
Alcohols, Part I

59m 52s

Intro
0:00
Alcohols
0:11
Attributes of Alcohols
0:12
Boiling Points
2:00
Water Solubility
5:00
Water Solubility (Like Dissolves Like)
5:01
Acidity of Alcohols
9:39
Comparison of Alcohols Acidity
9:41
Preparation of Alkoxides
13:03
Using Strong Base Like Sodium Hydride
13:04
Using Redox Reaction
15:36
Preparation of Alkoxides
17:41
Using K°
17:42
Phenols Are More Acidic Than Other Alcohols
19:51
Synthesis of Alcohols, ROH
21:43
Synthesis of Alcohols from Alkyl Halides, RX (SN2 or SN1)
21:44
Synthesis of Alcohols, ROH
25:08
Unlikely on 2° RX (E2 Favored)
25:09
Impossible on 3° RX (E2) and Phenyl/Vinyl RX (N/R)
25:47
Synthesis of Alcohols, ROH
26:26
SN1 with H₂O 'Solvolysis' or 'Hydrolysis'
26:27
Carbocation Can Rearrange
29:00
Synthesis of Alcohols, ROH
30:08
Synthesis of Alcohols From Alkenes: Hydration
30:09
Synthesis of Alcohols From Alkenes: Oxidation/Diol
32:20
Synthesis of Alcohols, ROH
33:14
Synthesis of Alcohols From Ketones and Aldehydes
33:15
Organometallic Reagents: Preparation
37:03
Grignard (RMgX)
37:04
Organolithium (Rli)
40:03
Organometallic Reagents: Reactions
41:45
Reactions of Organometallic Reagents
41:46
Organometallic Reagents: Reactions as Strong Nu:
46:40
Example 1: Reactions as Strong Nu:
46:41
Example 2: Reactions as Strong Nu:
48:57
Hydride Nu:
50:52
Hydride Nu:
50:53
Examples
53:34
Predict 1
53:35
Predict 2
54:45
Examples
56:43
Transform
56:44
Provide Starting Material
58:18
Alcohols, Part II

45m 35s

Intro
0:00
Oxidation Reactions
0:08
Oxidizing Agents: Jones, PCC, Swern
0:09
'Jones' Oxidation
0:43
Example 1: Predict Oxidation Reactions
2:29
Example 2: Predict Oxidation Reactions
3:00
Oxidation Reactions
4:11
Selective Oxidizing Agents (PCC and Swern)
4:12
PCC (Pyridiniym Chlorochromate)
5:10
Swern Oxidation
6:05
General [ox] Mechanism
8:32
General [ox] Mechanism
8:33
Oxidation of Alcohols
10:11
Example 1: Oxidation of Alcohols
10:12
Example 2: Oxidation of Alcohols
11:20
Example 3: Oxidation of Alcohols
11:46
Example
13:09
Predict: PCC Oxidation Reactions
13:10
Tosylation of Alcohols
15:22
Introduction to Tosylation of Alcohols
15:23
Example
21:08
Example: Tosylation of Alcohols
21:09
Reductions of Alcohols
23:39
Reductions of Alcohols via SN2 with Hydride
24:22
Reductions of Alcohols via Dehydration
27:12
Conversion of Alcohols to Alkyl Halides
30:12
Conversion of Alcohols to Alkyl Halides via Tosylate
30:13
Conversion of Alcohols to Alkyl Halides
31:17
Using HX
31:18
Mechanism
32:09
Conversion of Alcohols to Alkyl Halides
35:43
Reagents that Provide LG and Nu: in One 'Pot'
35:44
General Mechanisms
37:44
Example 1: General Mechanisms
37:45
Example 2: General Mechanisms
39:25
Example
41:04
Transformation of Alcohols
41:05
V. Ethers, Thiols, Thioethers, & Ketones
Ethers

1h 34m 45s

Intro
0:00
Ethers
0:11
Overview of Ethers
0:12
Boiling Points
1:37
Ethers
4:34
Water Solubility (Grams per 100mL H₂O)
4:35
Synthesis of Ethers
7:53
Williamson Ether Synthesis
7:54
Example: Synthesis of Ethers
9:23
Synthesis of Ethers
10:27
Example: Synthesis of Ethers
10:28
Intramolecular SN2
13:04
Planning an Ether Synthesis
14:45
Example 1: Planning an Ether Synthesis
14:46
Planning an Ether Synthesis
16:16
Example 2: Planning an Ether Synthesis
16:17
Planning an Ether Synthesis
22:04
Example 3: Synthesize Dipropyl Ether
22:05
Planning an Ether Synthesis
26:01
Example 4: Transform
26:02
Synthesis of Epoxides
30:05
Synthesis of Epoxides Via Williamson Ether Synthesis
30:06
Synthesis of Epoxides Via Oxidation
32:42
Reaction of Ethers
33:35
Reaction of Ethers
33:36
Reactions of Ethers with HBr or HI
34:44
Reactions of Ethers with HBr or HI
34:45
Mechanism
35:25
Epoxide Ring-Opening Reaction
39:25
Epoxide Ring-Opening Reaction
39:26
Example: Epoxide Ring-Opening Reaction
42:42
Acid-Catalyzed Epoxide Ring Opening
44:16
Acid-Catalyzed Epoxide Ring Opening Mechanism
44:17
Acid-Catalyzed Epoxide Ring Opening
50:13
Acid-Catalyzed Epoxide Ring Opening Mechanism
50:14
Catalyst Needed for Ring Opening
53:34
Catalyst Needed for Ring Opening
53:35
Stereochemistry of Epoxide Ring Opening
55:56
Stereochemistry: SN2 Mechanism
55:57
Acid or Base Mechanism?
58:30
Example
1:01:03
Transformation
1:01:04
Regiochemistry of Epoxide Ring Openings
1:05:29
Regiochemistry of Epoxide Ring Openings in Base
1:05:30
Regiochemistry of Epoxide Ring Openings in Acid
1:07:34
Example
1:10:26
Example 1: Epoxide Ring Openings in Base
1:10:27
Example 2: Epoxide Ring Openings in Acid
1:12:50
Reactions of Epoxides with Grignard and Hydride
1:15:35
Reactions of Epoxides with Grignard and Hydride
1:15:36
Example
1:21:47
Example: Ethers
1:21:50
Example
1:27:01
Example: Synthesize
1:27:02
Thiols and Thioethers

16m 50s

Intro
0:00
Thiols and Thioethers
0:10
Physical Properties
0:11
Reactions Can Be Oxidized
2:16
Acidity of Thiols
3:11
Thiols Are More Acidic Than Alcohols
3:12
Synthesis of Thioethers
6:44
Synthesis of Thioethers
6:45
Example
8:43
Example: Synthesize the Following Target Molecule
8:44
Example
14:18
Example: Predict
14:19
Ketones

2h 18m 12s

Intro
0:00
Aldehydes & Ketones
0:11
The Carbonyl: Resonance & Inductive
0:12
Reactivity
0:50
The Carbonyl
2:35
The Carbonyl
2:36
Carbonyl FG's
4:10
Preparation/Synthesis of Aldehydes & Ketones
6:18
Oxidation of Alcohols
6:19
Ozonolysis of Alkenes
7:16
Hydration of Alkynes
8:01
Reaction with Hydride Nu:
9:00
Reaction with Hydride Nu:
9:01
Reaction with Carbon Nu:
11:29
Carbanions: Acetylide
11:30
Carbanions: Cyanide
14:23
Reaction with Carbon Nu:
15:32
Organometallic Reagents (RMgX, Rli)
15:33
Retrosynthesis of Alcohols
17:04
Retrosynthesis of Alcohols
17:05
Example
19:30
Example: Transform
19:31
Example
22:57
Example: Transform
22:58
Example
28:19
Example: Transform
28:20
Example
33:36
Example: Transform
33:37
Wittig Reaction
37:39
Wittig Reaction: A Resonance-Stabilized Carbanion (Nu:)
37:40
Wittig Reaction: Mechanism
39:51
Preparation of Wittig Reagent
41:58
Two Steps From RX
41:59
Example: Predict
45:02
Wittig Retrosynthesis
46:19
Wittig Retrosynthesis
46:20
Synthesis
48:09
Reaction with Oxygen Nu:
51:21
Addition of H₂O
51:22
Exception: Formaldehyde is 99% Hydrate in H₂O Solution
54:10
Exception: Hydrate is Favored if Partial Positive Near Carbonyl
55:26
Reaction with Oxygen Nu:
57:45
Addition of ROH
57:46
TsOH: Tosic Acid
58:28
Addition of ROH Cont.
59:09
Example
1:01:43
Predict
1:01:44
Mechanism
1:03:08
Mechanism for Acetal Formation
1:04:10
Mechanism for Acetal Formation
1:04:11
What is a CTI?
1:15:04
Tetrahedral Intermediate
1:15:05
Charged Tetrahedral Intermediate
1:15:45
CTI: Acid-cat
1:16:10
CTI: Base-cat
1:17:01
Acetals & Cyclic Acetals
1:17:49
Overall
1:17:50
Cyclic Acetals
1:18:46
Hydrolysis of Acetals: Regenerates Carbonyl
1:20:01
Hydrolysis of Acetals: Regenerates Carbonyl
1:20:02
Mechanism
1:22:08
Reaction with Nitrogen Nu:
1:30:11
Reaction with Nitrogen Nu:
1:30:12
Example
1:32:18
Mechanism of Imine Formation
1:33:24
Mechanism of Imine Formation
1:33:25
Oxidation of Aldehydes
1:38:12
Oxidation of Aldehydes 1
1:38:13
Oxidation of Aldehydes 2
1:39:52
Oxidation of Aldehydes 3
1:40:10
Reductions of Ketones and Aldehydes
1:40:54
Reductions of Ketones and Aldehydes
1:40:55
Hydride/ Workup
1:41:22
Raney Nickel
1:42:07
Reductions of Ketones and Aldehydes
1:43:24
Clemmensen Reduction & Wolff-Kishner Reduction
1:43:40
Acetals as Protective Groups
1:46:50
Acetals as Protective Groups
1:46:51
Example
1:50:39
Example: Consider the Following Synthesis
1:50:40
Protective Groups
1:54:47
Protective Groups
1:54:48
Example
1:59:02
Example: Transform
1:59:03
Example: Another Route
2:04:54
Example: Transform
2:08:49
Example
2:08:50
Transform
2:08:51
Example
2:11:05
Transform
2:11:06
Example
2:13:45
Transform
2:13:46
Example
2:15:43
Provide the Missing Starting Material
2:15:44
VI. Organic Transformation Practice
Transformation Practice Problems

38m 58s

Intro
0:00
Practice Problems
0:33
Practice Problem 1: Transform
0:34
Practice Problem 2: Transform
3:57
Practice Problems
7:49
Practice Problem 3: Transform
7:50
Practice Problems
15:32
Practice Problem 4: Transform
15:34
Practice Problem 5: Transform
20:15
Practice Problems
24:08
Practice Problem 6: Transform
24:09
Practice Problem 7: Transform
29:27
Practice Problems
33:08
Practice Problem 8: Transform
33:09
Practice Problem 9: Transform
35:23
VII. Carboxylic Acids
Carboxylic Acids

1h 17m 51s

Intro
0:00
Review Reactions of Ketone/Aldehyde
0:06
Carbonyl Reactivity
0:07
Nu: = Hydride (Reduction)
1:37
Nu: = Grignard
2:08
Review Reactions of Ketone/Aldehyde
2:53
Nu: = Alcohol
2:54
Nu: = Amine
3:46
Carboxylic Acids and Their Derivatives
4:37
Carboxylic Acids and Their Derivatives
4:38
Ketone vs. Ester Reactivity
6:33
Ketone Reactivity
6:34
Ester Reactivity
6:55
Carboxylic Acids and Their Derivatives
7:30
Acid Halide, Anhydride, Ester, Amide, and Nitrile
7:43
General Reactions of Acarboxylic Acid Derivatives
9:22
General Reactions of Acarboxylic Acid Derivatives
9:23
Physical Properties of Carboxylic Acids
12:16
Acetic Acid
12:17
Carboxylic Acids
15:46
Aciditiy of Carboxylic Acids, RCO₂H
17:45
Alcohol
17:46
Carboxylic Acid
19:21
Aciditiy of Carboxylic Acids, RCO₂H
21:31
Aciditiy of Carboxylic Acids, RCO₂H
21:32
Aciditiy of Carboxylic Acids, RCO₂H
24:48
Example: Which is the Stronger Acid?
24:49
Aciditiy of Carboxylic Acids, RCO₂H
30:06
Inductive Effects Decrease with Distance
30:07
Preparation of Carboxylic Acids, RCO₂H
31:55
A) By Oxidation
31:56
Preparation of Carboxylic Acids, RCO₂H
34:37
Oxidation of Alkenes/Alkynes - Ozonolysis
34:38
Preparation of Carboxylic Acids, RCO₂H
36:17
B) Preparation of RCO₂H from Organometallic Reagents
36:18
Preparation of Carboxylic Acids, RCO₂H
38:02
Example: Preparation of Carboxylic Acids
38:03
Preparation of Carboxylic Acids, RCO₂H
40:38
C) Preparation of RCO₂H by Hydrolysis of Carboxylic Acid Derivatives
40:39
Hydrolysis Mechanism
42:19
Hydrolysis Mechanism
42:20
Mechanism: Acyl Substitution (Addition/Elimination)
43:05
Hydrolysis Mechanism
47:27
Substitution Reaction
47:28
RO is Bad LG for SN1/SN2
47:39
RO is okay LG for Collapse of CTI
48:31
Hydrolysis Mechanism
50:07
Base-promoted Ester Hydrolysis (Saponification)
50:08
Applications of Carboxylic Acid Derivatives:
53:10
Saponification Reaction
53:11
Ester Hydrolysis
57:15
Acid-Catalyzed Mechanism
57:16
Ester Hydrolysis Requires Acide or Base
1:03:06
Ester Hydrolysis Requires Acide or Base
1:03:07
Nitrile Hydrolysis
1:05:22
Nitrile Hydrolysis
1:05:23
Nitrile Hydrolysis Mechanism
1:06:53
Nitrile Hydrolysis Mechanism
1:06:54
Use of Nitriles in Synthesis
1:12:39
Example: Nitirles in Synthesis
1:12:40
Carboxylic Acid Derivatives

1h 21m 4s

Intro
0:00
Carboxylic Acid Derivatives
0:05
Carboxylic Acid Derivatives
0:06
General Structure
1:00
Preparation of Carboxylic Acid Derivatives
1:19
Which Carbonyl is the Better E+?
1:20
Inductive Effects
1:54
Resonance
3:23
Preparation of Carboxylic Acid Derivatives
6:52
Which is Better E+, Ester or Acid Chloride?
6:53
Inductive Effects
7:02
Resonance
7:20
Preparation of Carboxylic Acid Derivatives
10:45
Which is Better E+, Carboxylic Acid or Anhydride?
10:46
Inductive Effects & Resonance
11:00
Overall: Order of Electrophilicity and Leaving Group
14:49
Order of Electrophilicity and Leaving Group
14:50
Example: Acid Chloride
16:26
Example: Carboxylate
19:17
Carboxylic Acid Derivative Interconversion
20:53
Carboxylic Acid Derivative Interconversion
20:54
Preparation of Acid Halides
24:31
Preparation of Acid Halides
24:32
Preparation of Anhydrides
25:45
A) Dehydration of Acids (For Symmetrical Anhydride)
25:46
Preparation of Anhydrides
27:29
Example: Dehydration of Acids
27:30
Preparation of Anhydrides
29:16
B) From an Acid Chloride (To Make Mixed Anhydride)
29:17
Mechanism
30:03
Preparation of Esters
31:53
A) From Acid Chloride or Anhydride
31:54
Preparation of Esters
33:48
B) From Carboxylic Acids (Fischer Esterification)
33:49
Mechanism
36:55
Preparations of Esters
41:38
Example: Predict the Product
41:39
Preparation of Esters
43:17
C) Transesterification
43:18
Mechanism
45:17
Preparation of Esters
47:58
D) SN2 with Carboxylate
47:59
Mechanism: Diazomethane
49:28
Preparation of Esters
51:01
Example: Transform
51:02
Preparation of Amides
52:27
A) From an Acid Cl or Anhydride
52:28
Preparations of Amides
54:47
B) Partial Hydrolysis of Nitriles
54:48
Preparation of Amides
56:11
Preparation of Amides: Find Alternate Path
56:12
Preparation of Amides
59:04
C) Can't be Easily Prepared from RCO₂H Directly
59:05
Reactions of Carboxylic Acid Derivatives with Nucleophiles
1:01:41
A) Hydride Nu: Review
1:01:42
A) Hydride Nu: Sodium Borohydride + Ester
1:02:43
Reactions of Carboxylic Acid Derivatives with Nucleophiles
1:03:57
Lithium Aluminum Hydride (LAH)
1:03:58
Mechanism
1:04:29
Summary of Hydride Reductions
1:07:09
Summary of Hydride Reductions 1
1:07:10
Summary of Hydride Reductions 2
1:07:36
Hydride Reduction of Amides
1:08:12
Hydride Reduction of Amides Mechanism
1:08:13
Reaction of Carboxylic Acid Derivatives with Organometallics
1:12:04
Review 1
1:12:05
Review 2
1:12:50
Reaction of Carboxylic Acid Derivatives with Organometallics
1:14:22
Example: Lactone
1:14:23
Special Hydride Nu: Reagents
1:16:34
Diisobutylaluminum Hydride
1:16:35
Example
1:17:25
Other Special Hydride
1:18:41
Addition of Organocuprates to Acid Chlorides
1:19:07
Addition of Organocuprates to Acid Chlorides
1:19:08
VIII. Enols & Enolates
Enols and Enolates, Part 1

1h 26m 22s

Intro
0:00
Enols and Enolates
0:09
The Carbonyl
0:10
Keto-Enol Tautomerization
1:17
Keto-Enol Tautomerization Mechanism
2:28
Tautomerization Mechanism (2 Steps)
2:29
Keto-Enol Tautomerization Mechanism
5:15
Reverse Reaction
5:16
Mechanism
6:07
Formation of Enolates
7:27
Why is a Ketone's α H's Acidic?
7:28
Formation of Other Carbanions
10:05
Alkyne
10:06
Alkane and Alkene
10:53
Formation of an Enolate: Choice of Base
11:27
Example: Choice of Base
11:28
Formation of an Enolate: Choice of Base
13:56
Deprotonate, Stronger Base, and Lithium Diisopropyl Amide (LDA)
13:57
Formation of an Enolate: Choice of Base
15:48
Weaker Base & 'Active' Methylenes
15:49
Why Use NaOEt instead of NaOH?
19:01
Other Acidic 'α' Protons
20:30
Other Acidic 'α' Protons
20:31
Why is an Ester Less Acidic than a Ketone?
24:10
Other Acidic 'α' Protons
25:19
Other Acidic 'α' Protons Continue
25:20
How are Enolates Used
25:54
Enolates
25:55
Possible Electrophiles
26:21
Alkylation of Enolates
27:56
Alkylation of Enolates
27:57
Resonance Form
30:03
α-Halogenation
32:17
α-Halogenation
32:18
Iodoform Test for Methyl Ketones
33:47
α-Halogenation
35:55
Acid-Catalyzed
35:57
Mechanism: 1st Make Enol (2 Steps)
36:14
Whate Other Eloctrophiles ?
39:17
Aldol Condensation
39:38
Aldol Condensation
39:39
Aldol Mechanism
41:26
Aldol Mechanism: In Base, Deprotonate First
41:27
Aldol Mechanism
45:28
Mechanism for Loss of H₂O
45:29
Collapse of CTI and β-elimination Mechanism
47:51
Loss of H₂0 is not E2!
48:39
Aldol Summary
49:53
Aldol Summary
49:54
Base-Catalyzed Mechanism
52:34
Acid-Catalyzed Mechansim
53:01
Acid-Catalyzed Aldol Mechanism
54:01
First Step: Make Enol
54:02
Acid-Catalyzed Aldol Mechanism
56:54
Loss of H₂0 (β elimination)
56:55
Crossed/Mixed Aldol
1:00:55
Crossed/Mixed Aldol & Compound with α H's
1:00:56
Ketone vs. Aldehyde
1:02:30
Crossed/Mixed Aldol & Compound with α H's Continue
1:03:10
Crossed/Mixed Aldol
1:05:21
Mixed Aldol: control Using LDA
1:05:22
Crossed/Mixed Aldol Retrosynthesis
1:08:53
Example: Predic Aldol Starting Material (Aldol Retrosyntheiss)
1:08:54
Claisen Condensation
1:12:54
Claisen Condensation (Aldol on Esters)
1:12:55
Claisen Condensation
1:19:52
Example 1: Claisen Condensation
1:19:53
Claisen Condensation
1:22:48
Example 2: Claisen Condensation
1:22:49
Enols and Enolates, Part 2

50m 57s

Intro
0:00
Conjugate Additions
0:06
α, β-unsaturated Carbonyls
0:07
Conjugate Additions
1:50
'1,2-addition'
1:51
'1,-4-addition' or 'Conjugate Addition'
2:24
Conjugate Additions
4:53
Why can a Nu: Add to this Alkene?
4:54
Typical Alkene
5:09
α, β-unsaturated Alkene
5:39
Electrophilic Alkenes: Michael Acceptors
6:35
Other 'Electrophilic' Alkenes (Called 'Michael Acceptors)
6:36
1,4-Addition of Cuprates (R2CuLi)
8:29
1,4-Addition of Cuprates (R2CuLi)
8:30
1,4-Addition of Cuprates (R2CuLi)
11:23
Use Cuprates in Synthesis
11:24
Preparation of Cuprates
12:25
Prepare Organocuprate From Organolithium
12:26
Cuprates Also Do SN2 with RX E+ (Not True for RMgX, RLi)
13:06
1,4-Addition of Enolates: Michael Reaction
13:50
1,4-Addition of Enolates: Michael Reaction
13:51
Mechanism
15:57
1,4-Addition of Enolates: Michael Reaction
18:47
Example: 1,4-Addition of Enolates
18:48
1,4-Addition of Enolates: Michael Reaction
21:02
Michael Reaction, Followed by Intramolecular Aldol
21:03
Mechanism of the Robinson Annulation
24:26
Mechanism of the Robinson Annulation
24:27
Enols and Enolates: Advanced Synthesis Topics
31:10
Stablized Enolates and the Decarboxylation Reaction
31:11
Mechanism: A Pericyclic Reaction
32:08
Enols and Enolates: Advanced Synthesis Topics
33:32
Example: Advance Synthesis
33:33
Enols and Enolates: Advanced Synthesis Topics
36:10
Common Reagents: Diethyl Malonate
36:11
Common Reagents: Ethyl Acetoacetate
37:27
Enols and Enolates: Advanced Synthesis Topics
38:06
Example: Transform
38:07
Advanced Synthesis Topics: Enamines
41:52
Enamines
41:53
Advanced Synthesis Topics: Enamines
43:06
Reaction with Ketone/Aldehyde
43:07
Example
44:08
Advanced Synthesis Topics: Enamines
45:31
Example: Use Enamines as Nu: (Like Enolate)
45:32
Advanced Synthesis Topics: Enamines
47:56
Example
47:58
IX. Aromatic Compounds
Aromatic Compounds: Structure

1h 59s

Intro
0:00
Aromatic Compounds
0:05
Benzene
0:06
3D Sketch
1:33
Features of Benzene
4:41
Features of Benzene
4:42
Aromatic Stability
6:41
Resonance Stabilization of Benzene
6:42
Cyclohexatriene
7:24
Benzene (Actual, Experimental)
8:11
Aromatic Stability
9:03
Energy Graph
9:04
Aromaticity Requirements
9:55
1) Cyclic and Planar
9:56
2) Contiguous p Orbitals
10:49
3) Satisfy Huckel's Rule
11:20
Example: Benzene
12:32
Common Aromatic Compounds
13:28
Example: Pyridine
13:29
Common Aromatic Compounds
16:25
Example: Furan
16:26
Common Aromatic Compounds
19:42
Example: Thiophene
19:43
Example: Pyrrole
20:18
Common Aromatic Compounds
21:09
Cyclopentadienyl Anion
21:10
Cycloheptatrienyl Cation
23:48
Naphthalene
26:04
Determining Aromaticity
27:28
Example: Which of the Following are Aromatic?
27:29
Molecular Orbital (MO) Theory
32:26
What's So Special About '4n + 2' Electrons?
32:27
π bond & Overlapping p Orbitals
32:53
Molecular Orbital (MO) Diagrams
36:56
MO Diagram: Benzene
36:58
Drawing MO Diagrams
44:26
Example: 3-Membered Ring
44:27
Example: 4-Membered Ring
46:04
Drawing MO Diagrams
47:51
Example: 5-Membered Ring
47:52
Example: 8-Membered Ring
49:32
Aromaticity and Reactivity
51:03
Example: Which is More Acidic?
51:04
Aromaticity and Reactivity
56:03
Example: Which has More Basic Nitrogen, Pyrrole or Pyridine?
56:04
Aromatic Compounds: Reactions, Part 1

1h 24m 4s

Intro
0:00
Reactions of Benzene
0:07
N/R as Alkenes
0:08
Substitution Reactions
0:50
Electrophilic Aromatic Substitution
1:24
Electrophilic Aromatic Substitution
1:25
Mechanism Step 1: Addition of Electrophile
2:08
Mechanism Step 2: Loss of H+
4:14
Electrophilic Aromatic Substitution on Substituted Benzenes
5:21
Electron Donating Group
5:22
Electron Withdrawing Group
8:02
Halogen
9:23
Effects of Electron-Donating Groups (EDG)
10:23
Effects of Electron-Donating Groups (EDG)
10:24
What Effect Does EDG (OH) Have?
11:40
Reactivity
13:03
Regioselectivity
14:07
Regioselectivity: EDG is o/p Director
14:57
Prove It! Add E+ and Look at Possible Intermediates
14:58
Is OH Good or Bad?
17:38
Effects of Electron-Withdrawing Groups (EWG)
20:20
What Effect Does EWG Have?
20:21
Reactivity
21:28
Regioselectivity
22:24
Regioselectivity: EWG is a Meta Director
23:23
Prove It! Add E+ and Look at Competing Intermediates
23:24
Carbocation: Good or Bad?
26:01
Effects of Halogens on EAS
28:33
Inductive Withdrawal of e- Density vs. Resonance Donation
28:34
Summary of Substituent Effects on EAS
32:33
Electron Donating Group
32:34
Electron Withdrawing Group
33:37
Directing Power of Substituents
34:35
Directing Power of Substituents
34:36
Example
36:41
Electrophiles for Electrophilic Aromatic Substitution
38:43
Reaction: Halogenation
38:44
Electrophiles for Electrophilic Aromatic Substitution
40:27
Reaction: Nitration
40:28
Electrophiles for Electrophilic Aromatic Substitution
41:45
Reaction: Sulfonation
41:46
Electrophiles for Electrophilic Aromatic Substitution
43:19
Reaction: Friedel-Crafts Alkylation
43:20
Electrophiles for Electrophilic Aromatic Substitution
45:43
Reaction: Friedel-Crafts Acylation
45:44
Electrophilic Aromatic Substitution: Nitration
46:52
Electrophilic Aromatic Substitution: Nitration
46:53
Mechanism
48:56
Nitration of Aniline
52:40
Nitration of Aniline Part 1
52:41
Nitration of Aniline Part 2: Why?
54:12
Nitration of Aniline
56:10
Workaround: Protect Amino Group as an Amide
56:11
Electrophilic Aromatic Substitution: Sulfonation
58:16
Electrophilic Aromatic Substitution: Sulfonation
58:17
Example: Transform
59:25
Electrophilic Aromatic Substitution: Friedel-Crafts Alkylation
1:02:24
Electrophilic Aromatic Substitution: Friedel-Crafts Alkylation
1:02:25
Example & Mechanism
1:03:37
Friedel-Crafts Alkylation Drawbacks
1:05:48
A) Can Over-React (Dialkylation)
1:05:49
Friedel-Crafts Alkylation Drawbacks
1:08:21
B) Carbocation Can Rearrange
1:08:22
Mechanism
1:09:33
Friedel-Crafts Alkylation Drawbacks
1:13:35
Want n-Propyl? Use Friedel-Crafts Acylation
1:13:36
Reducing Agents
1:16:45
Synthesis with Electrophilic Aromatic Substitution
1:18:45
Example: Transform
1:18:46
Synthesis with Electrophilic Aromatic Substitution
1:20:59
Example: Transform
1:21:00
Aromatic Compounds: Reactions, Part 2

59m 10s

Intro
0:00
Reagents for Electrophilic Aromatic Substitution
0:07
Reagents for Electrophilic Aromatic Substitution
0:08
Preparation of Diazonium Salt
2:12
Preparation of Diazonium Salt
2:13
Reagents for Sandmeyer Reactions
4:14
Reagents for Sandmeyer Reactions
4:15
Apply Diazonium Salt in Synthesis
6:20
Example: Transform
6:21
Apply Diazonium Salt in Synthesis
9:14
Example: Synthesize Following Target Molecule from Benzene or Toluene
9:15
Apply Diazonium Salt in Synthesis
14:56
Example: Transform
14:57
Reactions of Aromatic Substituents
21:56
A) Reduction Reactions
21:57
Reactions of Aromatic Substituents
23:24
B) Oxidations of Arenes
23:25
Benzylic [ox] Even Breaks C-C Bonds!
25:05
Benzylic Carbon Can't Be Quaternary
25:55
Reactions of Aromatic Substituents
26:21
Example
26:22
Review of Benzoic Acid Synthesis
27:34
Via Hydrolysis
27:35
Via Grignard
28:20
Reactions of Aromatic Substituents
29:15
C) Benzylic Halogenation
29:16
Radical Stabilities
31:55
N-bromosuccinimide (NBS)
32:23
Reactions of Aromatic Substituents
33:08
D) Benzylic Substitutions
33:09
Reactions of Aromatic Side Chains
37:08
Example: Transform
37:09
Nucleophilic Aromatic Substitution
43:13
Nucleophilic Aromatic Substitution
43:14
Nucleophilic Aromatic Substitution
47:08
Example
47:09
Mechanism
48:00
Nucleophilic Aromatic Substitution
50:43
Example
50:44
Nucleophilic Substitution: Benzyne Mechanism
52:46
Nucleophilic Substitution: Benzyne Mechanism
52:47
Nucleophilic Substitution: Benzyne Mechanism
57:31
Example: Predict Product
57:32
X. Dienes & Amines
Conjugated Dienes

1h 9m 12s

Intro
0:00
Conjugated Dienes
0:08
Conjugated π Bonds
0:09
Diene Stability
2:00
Diene Stability: Cumulated
2:01
Diene Stability: Isolated
2:37
Diene Stability: Conjugated
2:51
Heat of Hydrogenation
3:00
Allylic Carbocations and Radicals
5:15
Allylic Carbocations and Radicals
5:16
Electrophilic Additions to Dienes
7:00
Alkenes
7:01
Unsaturated Ketone
7:47
Electrophilic Additions to Dienes
8:28
Conjugated Dienes
8:29
Electrophilic Additions to Dienes
9:46
Mechanism (2-Steps): Alkene
9:47
Electrophilic Additions to Dienes
11:40
Mechanism (2-Steps): Diene
11:41
1,2 'Kinetic' Product
13:08
1,4 'Thermodynamic' Product
14:47
E vs. POR Diagram
15:50
E vs. POR Diagram
15:51
Kinetic vs. Thermodynamic Control
21:56
Kinetic vs. Thermodynamic Control
21:57
How? Reaction is Reversible!
23:51
1,2 (Less Stable product)
23:52
1,4 (More Stable Product)
25:16
Diels Alder Reaction
26:34
Diels Alder Reaction
26:35
Dienophiles (E+)
29:23
Dienophiles (E+)
29:24
Alkyne Diels-Alder Example
30:48
Example: Alkyne Diels-Alder
30:49
Diels-Alder Reaction: Dienes (Nu:)
32:22
Diels-Alder ReactionL Dienes (Nu:)
32:23
Diels-Alder Reaction: Dienes
33:51
Dienes Must Have 's-cis' Conformation
33:52
Example
35:25
Diels-Alder Reaction with Cyclic Dienes
36:08
Cyclic Dienes are Great for Diels-Alder Reaction
36:09
Cyclopentadiene
37:10
Diels-Alder Reaction: Bicyclic Products
40:50
Endo vs. Exo Terminology: Norbornane & Bicyclo Heptane
40:51
Example: Bicyclo Heptane
42:29
Diels-Alder Reaction with Cyclic Dienes
44:15
Example
44:16
Stereochemistry of the Diels-Alder Reaction
47:39
Stereochemistry of the Diels-Alder Reaction
47:40
Example
48:08
Stereochemistry of the Diels-Alder Reaction
50:21
Example
50:22
Regiochemistry of the Diels-Alder Reaction
52:42
Rule: 1,2-Product Preferred Over 1,3-Product
52:43
Regiochemistry of the Diels-Alder Reaction
54:18
Rule: 1,4-Product Preferred Over 1,3-Product
54:19
Regiochemistry of the Diels-Alder Reaction
55:02
Why 1,2-Product or 1,4-Product Favored?
55:03
Example
56:11
Diels-Alder Reaction
58:06
Example: Predict
58:07
Diels-Alder Reaction
1:01:27
Explain Why No Diels-Alder Reaction Takes Place in This Case
1:01:28
Diels-Alder Reaction
1:03:09
Example: Predict
1:03:10
Diels-Alder Reaction: Synthesis Problem
1:05:39
Diels-Alder Reaction: Synthesis Problem
1:05:40
Pericyclic Reactions and Molecular Orbital (MO) Theory

1h 21m 31s

Intro
0:00
Pericyclic Reactions
0:05
Pericyclic Reactions
0:06
Electrocyclic Reactions
1:19
Electrocyclic Reactions
1:20
Electrocyclic Reactions
3:13
Stereoselectivity
3:14
Electrocyclic Reactions
8:10
Example: Predict
8:11
Sigmatropic Rearrangements
12:29
Sigmatropic Rearrangements
12:30
Cope Rearrangement
14:44
Sigmatropic Rearrangements
16:44
Claisen Rearrangement 1
16:45
Claisen Rearrangement 2
17:46
Cycloaddition Reactions
19:22
Diels-Alder
19:23
1,3-Dipolar Cycloaddition
20:32
Cycloaddition Reactions: Stereochemistry
21:58
Cycloaddition Reactions: Stereochemistry
21:59
Cycloaddition Reactions: Heat or Light?
26:00
4+2 Cycloadditions
26:01
2+2 Cycloadditions
27:23
Molecular Orbital (MO) Theory of Chemical Reactions
29:26
Example 1: Molecular Orbital Theory of Bonding
29:27
Molecular Orbital (MO) Theory of Chemical Reactions
31:59
Example 2: Molecular Orbital Theory of Bonding
32:00
Molecular Orbital (MO) Theory of Chemical Reactions
33:33
MO Theory of Aromaticity, Huckel's Rule
33:34
Molecular Orbital (MO) Theory of Chemical Reactions
36:43
Review: Molecular Orbital Theory of Conjugated Systems
36:44
Molecular Orbital (MO) Theory of Chemical Reactions
44:56
Review: Molecular Orbital Theory of Conjugated Systems
44:57
Molecular Orbital (MO) Theory of Chemical Reactions
46:54
Review: Molecular Orbital Theory of Conjugated Systems
46:55
Molecular Orbital (MO) Theory of Chemical Reactions
48:36
Frontier Molecular Orbitals are Involved in Reactions
48:37
Examples
50:20
MO Theory of Pericyclic Reactions: The Woodward-Hoffmann Rules
51:51
Heat-promoted Pericyclic Reactions and Light-promoted Pericyclic Reactions
51:52
MO Theory of Pericyclic Reactions: The Woodward-Hoffmann Rules
53:42
Why is a [4+2] Cycloaddition Thermally Allowed While the [2+2] is Not?
53:43
MO Theory of Pericyclic Reactions: The Woodward-Hoffmann Rules
56:51
Why is a [2+2] Cycloaddition Photochemically Allowed?
56:52
Pericyclic Reaction Example I
59:16
Pericyclic Reaction Example I
59:17
Pericyclic Reaction Example II
1:07:40
Pericyclic Reaction Example II
1:07:41
Pericyclic Reaction Example III: Vitamin D - The Sunshine Vitamin
1:14:22
Pericyclic Reaction Example III: Vitamin D - The Sunshine Vitamin
1:14:23
Amines

34m 58s

Intro
0:00
Amines: Properties and Reactivity
0:04
Compare Amines to Alcohols
0:05
Amines: Lower Boiling Point than ROH
0:55
1) RNH₂ Has Lower Boiling Point than ROH
0:56
Amines: Better Nu: Than ROH
2:22
2) RNH₂ is a Better Nucleophile than ROH Example 1
2:23
RNH₂ is a Better Nucleophile than ROH Example 2
3:08
Amines: Better Nu: than ROH
3:47
Example
3:48
Amines are Good Bases
5:41
3) RNH₂ is a Good Base
5:42
Amines are Good Bases
7:06
Example 1
7:07
Example 2: Amino Acid
8:27
Alkyl vs. Aryl Amines
9:56
Example: Which is Strongest Base?
9:57
Alkyl vs. Aryl Amines
14:55
Verify by Comparing Conjugate Acids
14:56
Reaction of Amines
17:42
Reaction with Ketone/Aldehyde: 1° Amine (RNH₂)
17:43
Reaction of Amines
18:48
Reaction with Ketone/Aldehyde: 2° Amine (R2NH)
18:49
Use of Enamine: Synthetic Equivalent of Enolate
20:08
Use of Enamine: Synthetic Equivalent of Enolate
20:09
Reaction of Amines
24:10
Hofmann Elimination
24:11
Hofmann Elimination
26:16
Kinetic Product
26:17
Structure Analysis Using Hofmann Elimination
28:22
Structure Analysis Using Hofmann Elimination
28:23
Biological Activity of Amines
30:30
Adrenaline
31:07
Mescaline (Peyote Alkaloid)
31:22
Amino Acids, Amide, and Protein
32:14
Biological Activity of Amines
32:50
Morphine (Opium Alkaloid)
32:51
Epibatidine (Poison Dart Frog)
33:28
Nicotine
33:48
Choline (Nerve Impulse)
34:03
XI. Biomolecules & Polymers
Biomolecules

1h 53m 20s

Intro
0:00
Carbohydrates
1:11
D-glucose Overview
1:12
D-glucose: Cyclic Form (6-membered ring)
4:31
Cyclic Forms of Glucose: 6-membered Ring
8:24
α-D-glucopyranose & β-D-glucopyranose
8:25
Formation of a 5-Membered Ring
11:05
D-glucose: Formation of a 5-Membered Ring
11:06
Cyclic Forms of Glucose: 5-membered Ring
12:37
α-D-glucofuranose & β-D-glucofuranose
12:38
Carbohydrate Mechanism
14:03
Carbohydrate Mechanism
14:04
Reactions of Glucose: Acetal Formation
21:35
Acetal Formation: Methyl-α-D-glucoside
21:36
Hemiacetal to Acetal: Overview
24:58
Mechanism for Formation of Glycosidic Bond
25:51
Hemiacetal to Acetal: Mechanism
25:52
Formation of Disaccharides
29:34
Formation of Disaccharides
29:35
Some Polysaccharides: Starch
31:33
Amylose & Amylopectin
31:34
Starch: α-1,4-glycosidic Bonds
32:22
Properties of Starch Molecule
33:21
Some Polysaccharides: Cellulose
33:59
Cellulose: β-1,4-glycosidic bonds
34:00
Properties of Cellulose
34:59
Other Sugar-Containing Biomolecules
35:50
Ribonucleoside (RNA)
35:51
Deoxyribonucleoside (DMA)
36:59
Amino Acids & Proteins
37:32
α-amino Acids: Structure & Stereochemistry
37:33
Making a Protein (Condensation)
42:46
Making a Protein (Condensation)
42:47
Peptide Bond is Planar (Amide Resonance)
44:55
Peptide Bond is Planar (Amide Resonance)
44:56
Protein Functions
47:49
Muscle, Skin, Bones, Hair Nails
47:50
Enzymes
49:10
Antibodies
49:44
Hormones, Hemoglobin
49:58
Gene Regulation
50:20
Various Amino Acid Side Chains
50:51
Nonpolar
50:52
Polar
51:15
Acidic
51:24
Basic
51:55
Amino Acid Table
52:22
Amino Acid Table
52:23
Isoelectric Point (pI)
53:43
Isoelectric Point (pI) of Glycine
53:44
Isoelectric Point (pI) of Glycine: pH 11
56:42
Isoelectric Point (pI) of Glycine: pH 1
57:20
Isoelectric Point (pI), cont.
58:05
Asparatic Acid
58:06
Histidine
1:00:28
Isoelectric Point (pI), cont.
1:02:54
Example: What is the Net Charge of This Tetrapeptide at pH 6.0?
1:02:55
Nucleic Acids: Ribonucleosides
1:10:32
Nucleic Acids: Ribonucleosides
1:10:33
Nucleic Acids: Ribonucleotides
1:11:48
Ribonucleotides: 5' Phosphorylated Ribonucleosides
1:11:49
Ribonucleic Acid (RNA) Structure
1:12:35
Ribonucleic Acid (RNA) Structure
1:12:36
Nucleic Acids: Deoxyribonucleosides
1:14:08
Nucleic Acids: Deoxyribonucleosides
1:14:09
Deoxythymidine (T)
1:14:36
Nucleic Acids: Base-Pairing
1:15:17
Nucleic Acids: Base-Pairing
1:15:18
Double-Stranded Structure of DNA
1:18:16
Double-Stranded Structure of DNA
1:18:17
Model of DNA
1:19:40
Model of DNA
1:19:41
Space-Filling Model of DNA
1:20:46
Space-Filling Model of DNA
1:20:47
Function of RNA and DNA
1:23:06
DNA & Transcription
1:23:07
RNA & Translation
1:24:22
Genetic Code
1:25:09
Genetic Code
1:25:10
Lipids/Fats/Triglycerides
1:27:10
Structure of Glycerol
1:27:43
Saturated & Unsaturated Fatty Acids
1:27:51
Triglyceride
1:28:43
Unsaturated Fats: Lower Melting Points (Liquids/Oils)
1:29:15
Saturated Fat
1:29:16
Unsaturated Fat
1:30:10
Partial Hydrogenation
1:32:05
Saponification of Fats
1:35:11
Saponification of Fats
1:35:12
History of Soap
1:36:50
Carboxylate Salts form Micelles in Water
1:41:02
Carboxylate Salts form Micelles in Water
1:41:03
Cleaning Power of Micelles
1:42:21
Cleaning Power of Micelles
1:42:22
3-D Image of a Micelle
1:42:58
3-D Image of a Micelle
1:42:59
Synthesis of Biodiesel
1:44:04
Synthesis of Biodiesel
1:44:05
Phosphoglycerides
1:47:54
Phosphoglycerides
1:47:55
Cell Membranes Contain Lipid Bilayers
1:48:41
Cell Membranes Contain Lipid Bilayers
1:48:42
Bilayer Acts as Barrier to Movement In/Out of Cell
1:50:24
Bilayer Acts as Barrier to Movement In/Out of Cell
1:50:25
Organic Chemistry Meets Biology… Biochemistry!
1:51:12
Organic Chemistry Meets Biology… Biochemistry!
1:51:13
Polymers

45m 47s

Intro
0:00
Polymers
0:05
Monomer to Polymer: Vinyl Chloride to Polyvinyl Chloride
0:06
Polymer Properties
1:32
Polymer Properties
1:33
Natural Polymers: Rubber
2:30
Vulcanization
2:31
Natural Polymers: Polysaccharides
4:55
Example: Starch
4:56
Example: Cellulose
5:45
Natural Polymers: Proteins
6:07
Example: Keratin
6:08
DNA Strands
7:15
DNA Strands
7:16
Synthetic Polymers
8:30
Ethylene & Polyethylene: Lightweight Insulator & Airtight Plastic
8:31
Synthetic Organic Polymers
12:22
Polyethylene
12:28
Polyvinyl Chloride (PVC)
12:54
Polystyrene
13:28
Polyamide
14:34
Polymethyl Methacrylate
14:57
Kevlar
15:25
Synthetic Material Examples
16:30
How are Polymers Made?
21:00
Chain-growth Polymers Additions to Alkenes can be Radical, Cationic or Anionic
21:01
Chain Branching
22:34
Chain Branching
22:35
Special Reaction Conditions Prevent Branching
24:28
Ziegler-Natta Catalyst
24:29
Chain-Growth by Cationic Polymerization
27:35
Chain-Growth by Cationic Polymerization
27:36
Chain-Growth by Anionic Polymerization
29:35
Chain-Growth by Anionic Polymerization
29:36
Step-Growth Polymerization: Polyamides
32:16
Step-Growth Polymerization: Polyamides
32:17
Step-Growth Polymerization: Polyesters
34:23
Step-Growth Polymerization: Polyesters
34:24
Step-Growth Polymerization: Polycarbonates
35:56
Step-Growth Polymerization: Polycarbonates
35:57
Step-Growth Polymerization: Polyurethanes
37:18
Step-Growth Polymerization: Polyurethanes
37:19
Modifying Polymer Properties
39:35
Glass Transition Temperature
40:04
Crosslinking
40:42
Copolymers
40:58
Additives: Stabilizers
42:08
Additives: Flame Retardants
43:03
Additives: Plasticizers
43:41
Additives: Colorants
44:54
XII. Organic Synthesis
Organic Synthesis Strategies

2h 20m 24s

Intro
0:00
Organic Synthesis Strategies
0:15
Goal
0:16
Strategy
0:29
Example of a RetroSynthesis
1:30
Finding Starting Materials for Target Molecule
1:31
Synthesis Using Starting Materials
4:56
Synthesis of Alcohols by Functional Group Interconversion (FGI)
6:00
Synthesis of Alcohols by Functional Group Interconversion Overview
6:01
Alcohols by Reduction
7:43
Ketone to Alcohols
7:45
Aldehyde to Alcohols
8:26
Carboxylic Acid Derivative to Alcohols
8:36
Alcohols by Hydration of Alkenes
9:28
Hydration of Alkenes Using H₃O⁺
9:29
Oxymercuration-Demercuration
10:35
Hydroboration Oxidation
11:02
Alcohols by Substitution
11:42
Primary Alkyl Halide to Alcohols Using NaOH
11:43
Secondary Alkyl Halide to Alcohols Using Sodium Acetate
13:07
Tertiary Alkyl Halide to Alcohols Using H₂O
15:08
Synthesis of Alcohols by Forming a New C-C Bond
15:47
Recall: Alcohol & RMgBr
15:48
Retrosynthesis
17:28
Other Alcohol Disconnections
19:46
19:47
Synthesis Using PhMGgBr: Example 2
23:05
Synthesis of Alkyl Halides
26:06
Synthesis of Alkyl Halides Overview
26:07
Synthesis of Alkyl Halides by Free Radical Halogenation
27:04
Synthesis of Alkyl Halides by Free Radical Halogenation
27:05
Synthesis of Alkyl Halides by Substitution
29:06
Alcohol to Alkyl Halides Using HBr or HCl
29:07
Alcohol to Alkyl Halides Using SOCl₂
30:57
Alcohol to Alkyl Halides Using PBr₃ and Using P, I₂
31:03
Synthesis of Alkyl Halides by Addition
32:02
Alkene to Alkyl Halides Using HBr
32:03
Alkene to Alkyl Halides Using HBr & ROOR (Peroxides)
32:35
Example: Synthesis of Alkyl Halide
34:18
Example: Synthesis of Alkyl Halide
34:19
Synthesis of Ethers
39:25
Synthesis of Ethers
39:26
Example: Synthesis of an Ether
41:12
Synthesize TBME (t-butyl methyl ether) from Alcohol Starting Materials
41:13
Synthesis of Amines
46:05
Synthesis of Amines
46:06
Gabriel Synthesis of Amines
47:57
Gabriel Synthesis of Amines
47:58
Amines by SN2 with Azide Nu:
49:50
Amines by SN2 with Azide Nu:
49:51
Amines by SN2 with Cyanide Nu:
50:31
Amines by SN2 with Cyanide Nu:
50:32
Amines by Reduction of Amides
51:30
Amines by Reduction of Amides
51:31
Reductive Amination of Ketones/Aldehydes
52:42
Reductive Amination of Ketones/Aldehydes
52:43
Example : Synthesis of an Amine
53:47
Example 1: Synthesis of an Amine
53:48
Example 2: Synthesis of an Amine
56:16
Synthesis of Alkenes
58:20
Synthesis of Alkenes Overview
58:21
Synthesis of Alkenes by Elimination
59:04
Synthesis of Alkenes by Elimination Using NaOH & Heat
59:05
Synthesis of Alkenes by Elimination Using H₂SO₄ & Heat
59:57
Synthesis of Alkenes by Reduction
1:02:05
Alkyne to Cis Alkene
1:02:06
Alkyne to Trans Alkene
1:02:56
Synthesis of Alkenes by Wittig Reaction
1:03:46
Synthesis of Alkenes by Wittig Reaction
1:03:47
Retrosynthesis of an Alkene
1:05:35
Example: Synthesis of an Alkene
1:06:57
Example: Synthesis of an Alkene
1:06:58
Making a Wittig Reagent
1:10:31
Synthesis of Alkynes
1:13:09
Synthesis of Alkynes
1:13:10
Synthesis of Alkynes by Elimination (FGI)
1:13:42
First Step: Bromination of Alkene
1:13:43
Second Step: KOH Heat
1:14:22
Synthesis of Alkynes by Alkylation
1:15:02
Synthesis of Alkynes by Alkylation
1:15:03
Retrosynthesis of an Alkyne
1:16:18
Example: Synthesis of an Alkyne
1:17:40
Example: Synthesis of an Alkyne
1:17:41
Synthesis of Alkanes
1:20:52
Synthesis of Alkanes
1:20:53
Synthesis of Aldehydes & Ketones
1:21:38
Oxidation of Alcohol Using PCC or Swern
1:21:39
Oxidation of Alkene Using 1) O₃, 2)Zn
1:22:42
Reduction of Acid Chloride & Nitrile Using DiBAL-H
1:23:25
Hydration of Alkynes
1:24:55
Synthesis of Ketones by Acyl Substitution
1:26:12
Reaction with R'₂CuLi
1:26:13
Reaction with R'MgBr
1:27:13
Synthesis of Aldehydes & Ketones by α-Alkylation
1:28:00
Synthesis of Aldehydes & Ketones by α-Alkylation
1:28:01
Retrosynthesis of a Ketone
1:30:10
Acetoacetate Ester Synthesis of Ketones
1:31:05
Acetoacetate Ester Synthesis of Ketones: Step 1
1:31:06
Acetoacetate Ester Synthesis of Ketones: Step 2
1:32:13
Acetoacetate Ester Synthesis of Ketones: Step 3
1:32:50
Example: Synthesis of a Ketone
1:34:11
Example: Synthesis of a Ketone
1:34:12
Synthesis of Carboxylic Acids
1:37:15
Synthesis of Carboxylic Acids
1:37:16
Example: Synthesis of a Carboxylic Acid
1:37:59
Example: Synthesis of a Carboxylic Acid (Option 1)
1:38:00
Example: Synthesis of a Carboxylic Acid (Option 2)
1:40:51
Malonic Ester Synthesis of Carboxylic Acid
1:42:34
Malonic Ester Synthesis of Carboxylic Acid: Step 1
1:42:35
Malonic Ester Synthesis of Carboxylic Acid: Step 2
1:43:36
Malonic Ester Synthesis of Carboxylic Acid: Step 3
1:44:01
Example: Synthesis of a Carboxylic Acid
1:44:53
Example: Synthesis of a Carboxylic Acid
1:44:54
Synthesis of Carboxylic Acid Derivatives
1:48:05
Synthesis of Carboxylic Acid Derivatives
1:48:06
Alternate Ester Synthesis
1:48:58
Using Fischer Esterification
1:48:59
Using SN2 Reaction
1:50:18
Using Diazomethane
1:50:56
Using 1) LDA, 2) R'-X
1:52:15
Practice: Synthesis of an Alkyl Chloride
1:53:11
Practice: Synthesis of an Alkyl Chloride
1:53:12
Patterns of Functional Groups in Target Molecules
1:59:53
Recall: Aldol Reaction
1:59:54
β-hydroxy Ketone Target Molecule
2:01:12
α,β-unsaturated Ketone Target Molecule
2:02:20
Patterns of Functional Groups in Target Molecules
2:03:15
Recall: Michael Reaction
2:03:16
Retrosynthesis: 1,5-dicarbonyl Target Molecule
2:04:07
Patterns of Functional Groups in Target Molecules
2:06:38
Recall: Claisen Condensation
2:06:39
Retrosynthesis: β-ketoester Target Molecule
2:07:30
2-Group Target Molecule Summary
2:09:03
2-Group Target Molecule Summary
2:09:04
Example: Synthesis of Epoxy Ketone
2:11:19
Synthesize the Following Target Molecule from Cyclohexanone: Part 1 - Retrosynthesis
2:11:20
Synthesize the Following Target Molecule from Cyclohexanone: Part 2 - Synthesis
2:14:10
Example: Synthesis of a Diketone
2:16:57
Synthesis of a Diketone: Step 1 - Retrosynthesis
2:16:58
Synthesis of a Diketone: Step 2 - Synthesis
2:18:51
XII. Organic Synthesis & Organic Analysis
Organic Analysis: Classical & Modern Methods

46m 46s

Intro
0:00
Organic Analysis: Classical Methods
0:17
Classical Methods for Identifying Chemicals
0:18
Organic Analysis: Classical Methods
2:21
When is Structure Identification Needed?
2:22
Organic Analysis: Classical Methods
6:17
Classical Methods of Structure Identification: Physical Appearance
6:18
Classical Methods of Structure Identification: Physical Constants
6:42
Organic Analysis: Classical Methods
7:37
Classical Methods of Structure Identification: Solubility Tests - Water
7:38
Organic Analysis: Classical Methods
10:51
Classical Methods of Structure Identification: Solubility Tests - 5% aq. HCl Basic FG (Amines)
10:52
Organic Analysis: Classical Methods
11:50
Classical Methods of Structure Identification: Solubility Tests - 5% aq. NaOH Acidic FG (Carboxylic Acids, Phenols)
11:51
Organic Analysis: Classical Methods
13:28
Classical Methods of Structure Identification: Solubility Tests - 5% aq. NaHCO3 Strongly Acidic FG (Carboxylic Acids)
13:29
Organic Analysis: Classical Methods
15:35
Classical Methods of Structure Identification: Solubility Tests - Insoluble in All of the Above
15:36
Organic Analysis: Classical Methods
16:49
Classical Methods of Structure Identification: Idoform Test for Methyl Ketones
16:50
Organic Analysis: Classical Methods
22:02
Classical Methods of Structure Identification: Tollens' Test or Fehling's Solution for Aldehydes
22:03
Organic Analysis: Classical Methods
25:01
Useful Application of Classical Methods: Glucose Oxidase on Glucose Test Strips
25:02
Organic Analysis: Classical Methods
26:26
Classical Methods of Structure Identification: Starch-iodide Test
26:27
Organic Analysis: Classical Methods
28:22
Classical Methods of Structure Identification: Lucas Reagent to Determine Primary/Secondary/Tertiary Alcohol
28:23
Organic Analysis: Classical Methods
31:35
Classical Methods of Structure Identification: Silver Nitrate Test for Alkyl Halides
31:36
Organic Analysis: Classical Methods
33:23
Preparation of Derivatives
33:24
Organic Analysis: Modern Methods
36:55
Modern Methods of Chemical Characterization
36:56
Organic Analysis: Modern Methods
40:36
Checklist for Manuscripts Submitted to the ACS Journal Organic Letters
40:37
Organic Analysis: Modern Methods
42:39
Checklist for Manuscripts Submitted to the ACS Journal Organic Letters
42:40
Analysis of Stereochemistry

1h 2m 52s

Intro
0:00
Chirality & Optical Activity
0:32
Levorotatory & Dextrorotatory
0:33
Example: Optically Active?
2:22
Example: Optically Active?
2:23
Measurement of Specific Rotation, [α]
5:09
Measurement of Specific Rotation, [α]
5:10
Example: Calculation of Specific Rotation
8:56
Example: Calculation of Specific Rotation
8:57
Variability of Specific Rotation, [α]
12:52
Variability of Specific Rotation, [α]
12:53
Other Measures of Optical Activity: ORD and CD
15:04
Optical Rotary Dispersion (ORD)
15:05
Circular Dischroism (CD)
18:32
Circular Dischroism (CD)
18:33
Mixtures of Enantiomers
20:16
Racemic Mixtures
20:17
Unequal Mixtures of Enantiomers
21:36
100% ee
22:48
0% ee
23:34
Example: Definition of ee?
24:00
Example: Definition of ee?
24:01
Analysis of Optical Purity: [α]
27:47
[α] Measurement Can Be Used for Known Compounds
27:48
Analysis of Optical Purity: [α]
34:30
NMR Methods Using a Chiral Derivatizing Agent (CDA): Mosher's Reagent
34:31
Analysis of Optical Purity: [α]
40:01
NMR Methods Using a Chiral Derivatizing Agent (CDA): CDA Salt Formation
40:02
Analysis of Optical Purity: Chromatography
42:46
Chiral Chromatography
42:47
Stereochemistry Analysis by NMR: J Values (Coupling Constant)
51:28
NMR Methods for Structure Determination
51:29
Stereochemistry Analysis by NRM: NOE
57:00
NOE - Nuclear Overhauser Effect ( 2D Versions: NOESY or ROESY)
57:01
XIII. Spectroscopy
Infrared Spectroscopy, Part I

1h 4m

Intro
0:00
Infrared (IR) Spectroscopy
0:09
Introduction to Infrared (IR) Spectroscopy
0:10
Intensity of Absorption Is Proportional to Change in Dipole
3:08
IR Spectrum of an Alkane
6:08
Pentane
6:09
IR Spectrum of an Alkene
13:12
1-Pentene
13:13
IR Spectrum of an Alkyne
15:49
1-Pentyne
15:50
IR Spectrum of an Aromatic Compound
18:02
Methylbenzene
18:24
IR of Substituted Aromatic Compounds
24:04
IR of Substituted Aromatic Compounds
24:05
IR Spectrum of 1,2-Disubstituted Aromatic
25:30
1,2-dimethylbenzene
25:31
IR Spectrum of 1,3-Disubstituted Aromatic
27:15
1,3-dimethylbenzene
27:16
IR Spectrum of 1,4-Disubstituted Aromatic
28:41
1,4-dimethylbenzene
28:42
IR Spectrum of an Alcohol
29:34
1-pentanol
29:35
IR Spectrum of an Amine
32:39
1-butanamine
32:40
IR Spectrum of a 2° Amine
34:50
Diethylamine
34:51
IR Spectrum of a 3° Amine
35:47
Triethylamine
35:48
IR Spectrum of a Ketone
36:41
2-butanone
36:42
IR Spectrum of an Aldehyde
40:10
Pentanal
40:11
IR Spectrum of an Ester
42:38
Butyl Propanoate
42:39
IR Spectrum of a Carboxylic Acid
44:26
Butanoic Acid
44:27
Sample IR Correlation Chart
47:36
Sample IR Correlation Chart: Wavenumber and Functional Group
47:37
Predicting IR Spectra: Sample Structures
52:06
Example 1
52:07
Example 2
53:29
Example 3
54:40
Example 4
57:08
Example 5
58:31
Example 6
59:07
Example 7
1:00:52
Example 8
1:02:20
Infrared Spectroscopy, Part II

48m 34s

Intro
0:00
Interpretation of IR Spectra: a Basic Approach
0:05
Interpretation of IR Spectra: a Basic Approach
0:06
Other Peaks to Look for
3:39
Examples
5:17
Example 1
5:18
Example 2
9:09
Example 3
11:52
Example 4
14:03
Example 5
16:31
Example 6
19:31
Example 7
22:32
Example 8
24:39
IR Problems Part 1
28:11
IR Problem 1
28:12
IR Problem 2
31:14
IR Problem 3
32:59
IR Problem 4
34:23
IR Problem 5
35:49
IR Problem 6
38:20
IR Problems Part 2
42:36
IR Problem 7
42:37
IR Problem 8
44:02
IR Problem 9
45:07
IR Problems10
46:10
Nuclear Magnetic Resonance (NMR) Spectroscopy, Part I

1h 32m 14s

Intro
0:00
Purpose of NMR
0:14
Purpose of NMR
0:15
How NMR Works
2:17
How NMR Works
2:18
Information Obtained From a ¹H NMR Spectrum
5:51
No. of Signals, Integration, Chemical Shifts, and Splitting Patterns
5:52
Number of Signals in NMR (Chemical Equivalence)
7:52
Example 1: How Many Signals in ¹H NMR?
7:53
Example 2: How Many Signals in ¹H NMR?
9:36
Example 3: How Many Signals in ¹H NMR?
12:15
Example 4: How Many Signals in ¹H NMR?
13:47
Example 5: How Many Signals in ¹H NMR?
16:12
Size of Signals in NMR (Peak Area or Integration)
21:23
Size of Signals in NMR (Peak Area or Integration)
21:24
Using Integral Trails
25:15
Example 1: C₈H₁₈O
25:16
Example 2: C₃H₈O
27:17
Example 3: C₇H₈
28:21
Location of NMR Signal (Chemical Shift)
29:05
Location of NMR Signal (Chemical Shift)
29:06
¹H NMR Chemical Shifts
33:20
¹H NMR Chemical Shifts
33:21
¹H NMR Chemical Shifts (Protons on Carbon)
37:03
¹H NMR Chemical Shifts (Protons on Carbon)
37:04
Chemical Shifts of H's on N or O
39:01
Chemical Shifts of H's on N or O
39:02
Estimating Chemical Shifts
41:13
Example 1: Estimating Chemical Shifts
41:14
Example 2: Estimating Chemical Shifts
43:22
Functional Group Effects are Additive
45:28
Calculating Chemical Shifts
47:38
Methylene Calculation
47:39
Methine Calculation
48:20
Protons on sp³ Carbons: Chemical Shift Calculation Table
48:50
Example: Estimate the Chemical Shift of the Selected H
50:29
Effects of Resonance on Chemical Shifts
53:11
Example 1: Effects of Resonance on Chemical Shifts
53:12
Example 2: Effects of Resonance on Chemical Shifts
55:09
Example 3: Effects of Resonance on Chemical Shifts
57:08
Shape of NMR Signal (Splitting Patterns)
59:17
Shape of NMR Signal (Splitting Patterns)
59:18
Understanding Splitting Patterns: The 'n+1 Rule'
1:01:24
Understanding Splitting Patterns: The 'n+1 Rule'
1:01:25
Explanation of n+1 Rule
1:02:42
Explanation of n+1 Rule: One Neighbor
1:02:43
Explanation of n+1 Rule: Two Neighbors
1:06:23
Summary of Splitting Patterns
1:06:24
Summary of Splitting Patterns
1:10:45
Predicting ¹H NMR Spectra
1:10:46
Example 1: Predicting ¹H NMR Spectra
1:13:30
Example 2: Predicting ¹H NMR Spectra
1:19:07
Example 3: Predicting ¹H NMR Spectra
1:23:50
Example 4: Predicting ¹H NMR Spectra
1:29:27
Nuclear Magnetic Resonance (NMR) Spectroscopy, Part II

2h 3m 48s

Intro
0:00
¹H NMR Problem-Solving Strategies
0:18
Step 1: Analyze IR Spectrum (If Provided)
0:19
Step 2: Analyze Molecular Formula (If Provided)
2:06
Step 3: Draw Pieces of Molecule
3:49
Step 4: Confirm Pieces
6:30
Step 5: Put the Pieces Together!
7:23
Step 6: Check Your Answer!
8:21
Examples
9:17
Example 1: Determine the Structure of a C₉H₁₀O₂ Compound with the Following ¹H NMR Data
9:18
Example 2: Determine the Structure of a C₉H₁₀O₂ Compound with the Following ¹H NMR Data
17:27
¹H NMR Practice
20:57
¹H NMR Practice 1: C₁₀H₁₄
20:58
¹H NMR Practice 2: C₄H₈O₂
29:50
¹H NMR Practice 3: C₆H₁₂O₃
39:19
¹H NMR Practice 4: C₈H₁₈
50:19
More About Coupling Constants (J Values)
57:11
Vicinal (3-bond) and Geminal (2-bond)
57:12
Cyclohexane (ax-ax) and Cyclohexane (ax-eq) or (eq-eq)
59:50
Geminal (Alkene), Cis (Alkene), and Trans (Alkene)
1:02:40
Allylic (4-bond) and W-coupling (4-bond) (Rigid Structures Only)
1:04:05
¹H NMR Advanced Splitting Patterns
1:05:39
Example 1: ¹H NMR Advanced Splitting Patterns
1:05:40
Example 2: ¹H NMR Advanced Splitting Patterns
1:10:01
Example 3: ¹H NMR Advanced Splitting Patterns
1:13:45
¹H NMR Practice
1:22:53
¹H NMR Practice 5: C₁₁H₁₇N
1:22:54
¹H NMR Practice 6: C₉H₁₀O
1:34:04
¹³C NMR Spectroscopy
1:44:49
¹³C NMR Spectroscopy
1:44:50
¹³C NMR Chemical Shifts
1:47:24
¹³C NMR Chemical Shifts Part 1
1:47:25
¹³C NMR Chemical Shifts Part 2
1:48:59
¹³C NMR Practice
1:50:16
¹³C NMR Practice 1
1:50:17
¹³C NMR Practice 2
1:58:30
C-13 DEPT NMR Experiments

23m 10s

Intro
0:00
C-13 DEPT NMR Spectoscopy
0:13
Overview
0:14
C-13 DEPT NMR Spectoscopy, Cont.
3:31
Match C-13 Peaks to Carbons on Structure
3:32
C-13 DEPT NMR Spectoscopy, Cont.
8:46
Predict the DEPT-90 and DEPT-135 Spectra for the Given Compound
8:47
C-13 DEPT NMR Spectoscopy, Cont.
12:30
Predict the DEPT-90 and DEPT-135 Spectra for the Given Compound
12:31
C-13 DEPT NMR Spectoscopy, Cont.
17:19
Determine the Structure of an Unknown Compound using IR Spectrum and C-13 DEPT NMR
17:20
Two-Dimensional NMR Techniques: COSY

33m 39s

Intro
0:00
Two-Dimensional NMR Techniques: COSY
0:14
How Do We Determine Which Protons are Related in the NMR?
0:15
Two-Dimensional NMR Techniques: COSY
1:48
COSY Spectra
1:49
Two-Dimensional NMR Techniques: COSY
7:00
COSY Correlation
7:01
Two-Dimensional NMR Techniques: COSY
8:55
Complete the COSY NMR Spectrum for the Given Compoun
8:56
NMR Practice Problem
15:40
Provide a Structure for the Unknown Compound with the H NMR and COSY Spectra Shown
15:41
Two-Dimensional NMR Techniques: HETCOR & HMBC

15m 5s

Intro
0:00
HETCOR
0:15
Heteronuclear Correlation Spectroscopy
0:16
HETCOR
2:04
HETCOR Example
2:05
HMBC
11:07
Heteronuclear Multiple Bond Correlation
11:08
HMBC
13:14
HMB Example
13:15
Mass Spectrometry

1h 28m 35s

Intro
0:00
Introduction to Mass Spectrometry
0:37
Uses of Mass Spectrometry: Molecular Mass
0:38
Uses of Mass Spectrometry: Molecular Formula
1:04
Uses of Mass Spectrometry: Structural Information
1:21
Uses of Mass Spectrometry: In Conjunction with Gas Chromatography
2:03
Obtaining a Mass Spectrum
2:59
Obtaining a Mass Spectrum
3:00
The Components of a Mass Spectrum
6:44
The Components of a Mass Spectrum
6:45
What is the Mass of a Single Molecule
12:13
Example: CH₄
12:14
Example: ¹³CH₄
12:51
What Ratio is Expected for the Molecular Ion Peaks of C₂H₆?
14:20
Other Isotopes of High Abundance
16:30
Example: Cl Atoms
16:31
Example: Br Atoms
18:33
Mass Spectrometry of Chloroethane
19:22
Mass Spectrometry of Bromobutane
21:23
Isotopic Abundance can be Calculated
22:48
What Ratios are Expected for the Molecular Ion Peaks of CH₂Br₂?
22:49
Determining Molecular Formula from High-resolution Mass Spectrometry
26:53
Exact Masses of Various Elements
26:54
Fragmentation of various Functional Groups
28:42
What is More Stable, a Carbocation C⁺ or a Radical R?
28:43
Fragmentation is More Likely If It Gives Relatively Stable Carbocations and Radicals
31:37
Mass Spectra of Alkanes
33:15
Example: Hexane
33:16
Fragmentation Method 1
34:19
Fragmentation Method 2
35:46
Fragmentation Method 3
36:15
Mass of Common Fragments
37:07
Mass of Common Fragments
37:08
Mass Spectra of Alkanes
39:28
Mass Spectra of Alkanes
39:29
What are the Peaks at m/z 15 and 71 So Small?
41:01
Branched Alkanes
43:12
Explain Why the Base Peak of 2-methylhexane is at m/z 43 (M-57)
43:13
Mass Spectra of Alkenes
45:42
Mass Spectra of Alkenes: Remove 1 e⁻
45:43
Mass Spectra of Alkenes: Fragment
46:14
High-Energy Pi Electron is Most Likely Removed
47:59
Mass Spectra of Aromatic Compounds
49:01
Mass Spectra of Aromatic Compounds
49:02
Mass Spectra of Alcohols
51:32
Mass Spectra of Alcohols
51:33
Mass Spectra of Ethers
54:53
Mass Spectra of Ethers
54:54
Mass Spectra of Amines
56:49
Mass Spectra of Amines
56:50
Mass Spectra of Aldehydes & Ketones
59:23
Mass Spectra of Aldehydes & Ketones
59:24
McLafferty Rearrangement
1:01:29
McLafferty Rearrangement
1:01:30
Mass Spectra of Esters
1:04:15
Mass Spectra of Esters
1:01:16
Mass Spectrometry Discussion I
1:05:01
For the Given Molecule (M=58), Do You Expect the More Abundant Peak to Be m/z 15 or m/z 43?
1:05:02
Mass Spectrometry Discussion II
1:08:13
For the Given Molecule (M=74), Do You Expect the More Abundant Peak to Be m/z 31, m/z 45, or m/z 59?
1:08:14
Mass Spectrometry Discussion III
1:11:42
Explain Why the Mass Spectra of Methyl Ketones Typically have a Peak at m/z 43
1:11:43
Mass Spectrometry Discussion IV
1:14:46
In the Mass Spectrum of the Given Molecule (M=88), Account for the Peaks at m/z 45 and m/z 57
1:14:47
Mass Spectrometry Discussion V
1:18:25
How Could You Use Mass Spectrometry to Distinguish Between the Following Two Compounds (M=73)?
1:18:26
Mass Spectrometry Discussion VI
1:22:45
What Would be the m/z Ratio for the Fragment for the Fragment Resulting from a McLafferty Rearrangement for the Following Molecule (M=114)?
1:22:46
XIV. Organic Chemistry Lab
Completing the Reagent Table for Prelab

21m 9s

Intro
0:00
Sample Reagent Table
0:11
Reagent Table Overview
0:12
Calculate Moles of 2-bromoaniline
6:44
Calculate Molar Amounts of Each Reagent
9:20
Calculate Mole of NaNO₂
9:21
Calculate Moles of KI
10:33
Identify the Limiting Reagent
11:17
Which Reagent is the Limiting Reagent?
11:18
Calculate Molar Equivalents
13:37
Molar Equivalents
13:38
Calculate Theoretical Yield
16:40
Theoretical Yield
16:41
Calculate Actual Yield (%Yield)
18:30
Actual Yield (%Yield)
18:31
Introduction to Melting Points

16m 10s

Intro
0:00
Definition of a Melting Point (mp)
0:04
Definition of a Melting Point (mp)
0:05
Solid Samples Melt Gradually
1:49
Recording Range of Melting Temperature
2:04
Melting Point Theory
3:14
Melting Point Theory
3:15
Effects of Impurities on a Melting Point
3:57
Effects of Impurities on a Melting Point
3:58
Special Exception: Eutectic Mixtures
5:09
Freezing Point Depression by Solutes
5:39
Melting Point Uses
6:19
Solid Compound
6:20
Determine Purity of a Sample
6:42
Identify an Unknown Solid
7:06
Recording a Melting Point
9:03
Pack 1-3 mm of Dry Powder in MP Tube
9:04
Slowly Heat Sample
9:55
Record Temperature at First Sign of Melting
10:33
Record Temperature When Last Crystal Disappears
11:26
Discard MP Tube in Glass Waste
11:32
Determine Approximate MP
11:42
Tips, Tricks and Warnings
12:28
Use Small, Tightly Packed Sample
12:29
Be Sure MP Apparatus is Cool
12:45
Never Reuse a MP Tube
13:16
Sample May Decompose
13:30
If Pure Melting Point (MP) Doesn't Match Literature
14:20
Melting Point Lab

8m 17s

Intro
0:00
Melting Point Tubes
0:40
Melting Point Apparatus
3:42
Recording a melting Point
5:50
Introduction to Recrystallization

22m

Intro
0:00
Crystallization to Purify a Solid
0:10
Crude Solid
0:11
Hot Solution
0:20
Crystals
1:09
Supernatant Liquid
1:20
Theory of Crystallization
2:34
Theory of Crystallization
2:35
Analysis and Obtaining a Second Crop
3:40
Crystals → Melting Point, TLC
3:41
Supernatant Liquid → Crude Solid → Pure Solid
4:18
Crystallize Again → Pure Solid (2nd Crop)
4:32
Choosing a Solvent
5:19
1. Product is Very Soluble at High Temperatures
5:20
2. Product has Low Solubility at Low Temperatures
6:00
3. Impurities are Soluble at All Temperatures
6:16
Check Handbooks for Suitable Solvents
7:33
Why Isn't This Dissolving?!
8:46
If Solid Remains When Solution is Hot
8:47
Still Not Dissolved in Hot Solvent?
10:18
Where Are My Crystals?!
12:23
If No Crystals Form When Solution is Cooled
12:24
Still No Crystals?
14:59
Tips, Tricks and Warnings
16:26
Always Use a Boiling Chip or Stick!
16:27
Use Charcoal to Remove Colored Impurities
16:52
Solvent Pairs May Be Used
18:23
Product May 'Oil Out'
20:11
Recrystallization Lab

19m 7s

Intro
0:00
Step 1: Dissolving the Solute in the Solvent
0:12
Hot Filtration
6:33
Step 2: Cooling the Solution
8:01
Step 3: Filtering the Crystals
12:08
Step 4: Removing & Drying the Crystals
16:10
Introduction to Distillation

25m 54s

Intro
0:00
Distillation: Purify a Liquid
0:04
Simple Distillation
0:05
Fractional Distillation
0:55
Theory of Distillation
1:04
Theory of Distillation
1:05
Vapor Pressure and Volatility
1:52
Vapor Pressure
1:53
Volatile Liquid
2:28
Less Volatile Liquid
3:09
Vapor Pressure vs. Boiling Point
4:03
Vapor Pressure vs. Boiling Point
4:04
Increasing Vapor Pressure
4:38
The Purpose of Boiling Chips
6:46
The Purpose of Boiling Chips
6:47
Homogeneous Mixtures of Liquids
9:24
Dalton's Law
9:25
Raoult's Law
10:27
Distilling a Mixture of Two Liquids
11:41
Distilling a Mixture of Two Liquids
11:42
Simple Distillation: Changing Vapor Composition
12:06
Vapor & Liquid
12:07
Simple Distillation: Changing Vapor Composition
14:47
Azeotrope
18:41
Fractional Distillation: Constant Vapor Composition
19:42
Fractional Distillation: Constant Vapor Composition
19:43
Distillation Lab

24m 13s

Intro
0:00
Glassware Overview
0:04
Heating a Sample
3:09
Bunsen Burner
3:10
Heating Mantle 1
4:45
Heating Mantle 2
6:18
Hot Plate
7:10
Simple Distillation Lab
8:37
Fractional Distillation Lab
17:13
Removing the Distillation Set-Up
22:41
Introduction to TLC (Thin-Layer Chromatography)

28m 51s

Intro
0:00
Chromatography
0:06
Purification & Analysis
0:07
Types of Chromatography: Thin-layer, Column, Gas, & High Performance Liquid
0:24
Theory of Chromatography
0:44
Theory of Chromatography
0:45
Performing a Thin-layer Chromatography (TLC) Analysis
2:30
Overview: Thin-layer Chromatography (TLC) Analysis
2:31
Step 1: 'Spot' the TLC Plate
4:11
Step 2: Prepare the Developing Chamber
5:54
Step 3: Develop the TLC Plate
7:30
Step 4: Visualize the Spots
9:02
Step 5: Calculate the Rf for Each Spot
12:00
Compound Polarity: Effect on Rf
16:50
Compound Polarity: Effect on Rf
16:51
Solvent Polarity: Effect on Rf
18:47
Solvent Polarity: Effect on Rf
18:48
Example: EtOAc & Hexane
19:35
Other Types of Chromatography
22:27
Thin-layer Chromatography (TLC)
22:28
Column Chromatography
22:56
High Performance Liquid (HPLC)
23:59
Gas Chromatography (GC)
24:38
Preparative 'prep' Scale Possible
28:05
TLC Analysis Lab

20m 50s

Intro
0:00
Step 1: 'Spot' the TLC Plate
0:06
Step 2: Prepare the Developing Chamber
4:06
Step 3: Develop the TLC Plate
6:26
Step 4: Visualize the Spots
7:45
Step 5: Calculate the Rf for Each Spot
11:48
How to Make Spotters
12:58
TLC Plate
16:04
Flash Column Chromatography
17:11
Introduction to Extractions

34m 25s

Intro
0:00
Extraction Purify, Separate Mixtures
0:07
Adding a Second Solvent
0:28
Mixing Two Layers
0:38
Layers Settle
0:54
Separate Layers
1:05
Extraction Uses
1:20
To Separate Based on Difference in Solubility/Polarity
1:21
To Separate Based on Differences in Reactivity
2:11
Separate & Isolate
2:20
Theory of Extraction
3:03
Aqueous & Organic Phases
3:04
Solubility: 'Like Dissolves Like'
3:25
Separation of Layers
4:06
Partitioning
4:14
Distribution Coefficient, K
5:03
Solutes Partition Between Phases
5:04
Distribution Coefficient, K at Equilibrium
6:27
Acid-Base Extractions
8:09
Organic Layer
8:10
Adding Aqueous HCl & Mixing Two Layers
8:46
Neutralize (Adding Aqueous NaOH)
10:05
Adding Organic Solvent Mix Two Layers 'Back Extract'
10:24
Final Results
10:43
Planning an Acid-Base Extraction, Part 1
11:01
Solute Type: Neutral
11:02
Aqueous Solution: Water
13:40
Solute Type: Basic
14:43
Solute Type: Weakly Acidic
15:23
Solute Type: Acidic
16:12
Planning an Acid-Base Extraction, Part 2
17:34
Planning an Acid-Base Extraction
17:35
Performing an Extraction
19:34
Pour Solution into Sep Funnel
19:35
Add Second Liquid
20:07
Add Stopper, Cover with Hand, Remove from Ring
20:48
Tip Upside Down, Open Stopcock to Vent Pressure
21:00
Shake to Mix Two Layers
21:30
Remove Stopper & Drain Bottom Layer
21:40
Reaction Work-up: Purify, Isolate Product
22:03
Typical Reaction is Run in Organic Solvent
22:04
Starting a Reaction Work-up
22:33
Extracting the Product with Organic Solvent
23:17
Combined Extracts are Washed
23:40
Organic Layer is 'Dried'
24:23
Finding the Product
26:38
Which Layer is Which?
26:39
Where is My Product?
28:00
Tips, Tricks and Warnings
29:29
Leaking Sep Funnel
29:30
Caution When Mixing Layers & Using Ether
30:17
If an Emulsion Forms
31:51
Extraction Lab

14m 49s

Intro
0:00
Step 1: Preparing the Separatory Funnel
0:03
Step 2: Adding Sample
1:18
Step 3: Mixing the Two Layers
2:59
Step 4: Draining the Bottom Layers
4:59
Step 5: Performing a Second Extraction
5:50
Step 6: Drying the Organic Layer
7:21
Step 7: Gravity Filtration
9:35
Possible Extraction Challenges
12:55
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Lecture Comments (2)

1 answer

Last reply by: Professor Starkey
Wed Jul 1, 2015 12:55 AM

Post by Brandon Dorman on June 29, 2015

Hello,

Thanks for your videos. :)  They're great.

I understand that O is more electronegative and will react more than N. But I was confused by a problem I ran across.  This reaction was: (Ch3)2N- + H20 = (Ch3)2NH + OH-

I'm am confused why OH- isn't a stronger base than (Ch3)2N- since OH- is listed as a strong base. Shouldn't this equilibrium be predominantly to the left?

Biomolecules

Draw the product(s) for this reaction:
Draw the product(s) for this reaction:
Draw the 3-D representation α anomer for this glucose:

*These practice questions are only helpful when you work on them offline on a piece of paper and then use the solution steps function to check your answer.

Answer

Biomolecules

Lecture Slides are screen-captured images of important points in the lecture. Students can download and print out these lecture slide images to do practice problems as well as take notes while watching the lecture.

  1. Intro
    • Carbohydrates
    • Cyclic Forms of Glucose: 6-membered Ring
    • Formation of a 5-Membered Ring
    • Cyclic Forms of Glucose: 5-membered Ring
    • Carbohydrate Mechanism
    • Reactions of Glucose: Acetal Formation
    • Mechanism for Formation of Glycosidic Bond
    • Formation of Disaccharides
    • Some Polysaccharides: Starch
    • Some Polysaccharides: Cellulose
    • Other Sugar-Containing Biomolecules
    • Amino Acids & Proteins
    • Making a Protein (Condensation)
    • Peptide Bond is Planar (Amide Resonance)
    • Protein Functions
    • Various Amino Acid Side Chains
    • Amino Acid Table
    • Isoelectric Point (pI)
    • Isoelectric Point (pI), cont.
    • Isoelectric Point (pI), cont.
    • Nucleic Acids: Ribonucleosides
    • Nucleic Acids: Ribonucleotides
    • Ribonucleic Acid (RNA) Structure
    • Nucleic Acids: Deoxyribonucleosides
    • Nucleic Acids: Base-Pairing
    • Double-Stranded Structure of DNA
    • Model of DNA
    • Space-Filling Model of DNA
    • Function of RNA and DNA
    • Genetic Code
    • Lipids/Fats/Triglycerides
    • Unsaturated Fats: Lower Melting Points (Liquids/Oils)
    • Saponification of Fats
    • Carboxylate Salts form Micelles in Water
    • Cleaning Power of Micelles
    • 3-D Image of a Micelle
    • Synthesis of Biodiesel
    • Phosphoglycerides
    • Cell Membranes Contain Lipid Bilayers
    • Bilayer Acts as Barrier to Movement In/Out of Cell
    • Organic Chemistry Meets Biology… Biochemistry!
    • Intro 0:00
    • Carbohydrates 1:11
      • D-glucose Overview
      • D-glucose: Cyclic Form (6-membered ring)
    • Cyclic Forms of Glucose: 6-membered Ring 8:24
      • α-D-glucopyranose & β-D-glucopyranose
    • Formation of a 5-Membered Ring 11:05
      • D-glucose: Formation of a 5-Membered Ring
    • Cyclic Forms of Glucose: 5-membered Ring 12:37
      • α-D-glucofuranose & β-D-glucofuranose
    • Carbohydrate Mechanism 14:03
      • Carbohydrate Mechanism
    • Reactions of Glucose: Acetal Formation 21:35
      • Acetal Formation: Methyl-α-D-glucoside
      • Hemiacetal to Acetal: Overview
    • Mechanism for Formation of Glycosidic Bond 25:51
      • Hemiacetal to Acetal: Mechanism
    • Formation of Disaccharides 29:34
      • Formation of Disaccharides
    • Some Polysaccharides: Starch 31:33
      • Amylose & Amylopectin
      • Starch: α-1,4-glycosidic Bonds
      • Properties of Starch Molecule
    • Some Polysaccharides: Cellulose 33:59
      • Cellulose: β-1,4-glycosidic bonds
      • Properties of Cellulose
    • Other Sugar-Containing Biomolecules 35:50
      • Ribonucleoside (RNA)
      • Deoxyribonucleoside (DMA)
    • Amino Acids & Proteins 37:32
      • α-amino Acids: Structure & Stereochemistry
    • Making a Protein (Condensation) 42:46
      • Making a Protein (Condensation)
    • Peptide Bond is Planar (Amide Resonance) 44:55
      • Peptide Bond is Planar (Amide Resonance)
    • Protein Functions 47:49
      • Muscle, Skin, Bones, Hair Nails
      • Enzymes
      • Antibodies
      • Hormones, Hemoglobin
      • Gene Regulation
    • Various Amino Acid Side Chains 50:51
      • Nonpolar
      • Polar
      • Acidic
      • Basic
    • Amino Acid Table 52:22
      • Amino Acid Table
    • Isoelectric Point (pI) 53:43
      • Isoelectric Point (pI) of Glycine
      • Isoelectric Point (pI) of Glycine: pH 11
      • Isoelectric Point (pI) of Glycine: pH 1
    • Isoelectric Point (pI), cont. 58:05
      • Asparatic Acid
      • Histidine
    • Isoelectric Point (pI), cont. 1:02:54
      • Example: What is the Net Charge of This Tetrapeptide at pH 6.0?
    • Nucleic Acids: Ribonucleosides 1:10:32
      • Nucleic Acids: Ribonucleosides
    • Nucleic Acids: Ribonucleotides 1:11:48
      • Ribonucleotides: 5' Phosphorylated Ribonucleosides
    • Ribonucleic Acid (RNA) Structure 1:12:35
      • Ribonucleic Acid (RNA) Structure
    • Nucleic Acids: Deoxyribonucleosides 1:14:08
      • Nucleic Acids: Deoxyribonucleosides
      • Deoxythymidine (T)
    • Nucleic Acids: Base-Pairing 1:15:17
      • Nucleic Acids: Base-Pairing
    • Double-Stranded Structure of DNA 1:18:16
      • Double-Stranded Structure of DNA
    • Model of DNA 1:19:40
      • Model of DNA
    • Space-Filling Model of DNA 1:20:46
      • Space-Filling Model of DNA
    • Function of RNA and DNA 1:23:06
      • DNA & Transcription
      • RNA & Translation
    • Genetic Code 1:25:09
      • Genetic Code
    • Lipids/Fats/Triglycerides 1:27:10
      • Structure of Glycerol
      • Saturated & Unsaturated Fatty Acids
      • Triglyceride
    • Unsaturated Fats: Lower Melting Points (Liquids/Oils) 1:29:15
      • Saturated Fat
      • Unsaturated Fat
      • Partial Hydrogenation
    • Saponification of Fats 1:35:11
      • Saponification of Fats
      • History of Soap
    • Carboxylate Salts form Micelles in Water 1:41:02
      • Carboxylate Salts form Micelles in Water
    • Cleaning Power of Micelles 1:42:21
      • Cleaning Power of Micelles
    • 3-D Image of a Micelle 1:42:58
      • 3-D Image of a Micelle
    • Synthesis of Biodiesel 1:44:04
      • Synthesis of Biodiesel
    • Phosphoglycerides 1:47:54
      • Phosphoglycerides
    • Cell Membranes Contain Lipid Bilayers 1:48:41
      • Cell Membranes Contain Lipid Bilayers
    • Bilayer Acts as Barrier to Movement In/Out of Cell 1:50:24
      • Bilayer Acts as Barrier to Movement In/Out of Cell
    • Organic Chemistry Meets Biology… Biochemistry! 1:51:12
      • Organic Chemistry Meets Biology… Biochemistry!

    Transcription: Biomolecules

    Hello; welcome back to Educator.0000

    Today, we are going to be talking about biologically interesting organic compounds, or we could call them biomolecules for short.0002

    Now, there is a reason that, if you are going to be studying biochemistry, you typically need an entire year of organic chemistry to prepare you for biochemistry; and that is because biochemistry is the study of organic molecules and organic reactions that are going on inside living systems.0008

    And so, much of it requires, not only an understanding of the structures of molecules, the stereochemistry, and so on, but also the reactivity of different functional groups.0025

    And so, today, we are going to be studying different classes of biologically relevant molecules, some of which you may have already seen a little bit before; but others--we are going to get into a lot more detail.0036

    And still, this is all at a level that is not at the biochemistry level; I am not a biochemist, and this is not a biochemistry course; but it is going to give you an introduction from an organic chemist's point of view, in terms of what the significant functional groups are, and seeing if we can understand a little bit of how these molecules come together and what behavior they might have in actual systems.0050

    So first, we will start looking at carbohydrates.0070

    Carbohydrates is another word...an example of carbohydrates are sugars; and so, we know of sugars; carbohydrates are one of the things that we can eat and digest as part of our diet, in addition to proteins and fats.0072

    And so, in fact, we are going to be talking about all three of those things today; so obviously, all of those components are significant when it comes to the metabolism of those compounds and converting those into energy for our bodies' use.0090

    This is a general structure of a sugar; there are lots of different sugars we can have; this one is described as a hexose, because it has 6 carbons.0102

    And it is also described as just a monosaccharide; we are going to see that these can form chains--they can link together to form a disaccharide, if we have two sugar units; and it could actually make long polymer chains--we call those polysaccharides.0113

    This is the structure of D-glucose; that is the sugar we know as blood sugar.0126

    If you are a diabetic, you have problems with insulin production and maintenance of a proper sugar level; it is the glucose in your blood that you are testing, any time you test your blood, and that you are trying to monitor and keep at an appropriate level.0131

    And so, glucose is a hexose--we see that up here; it has an aldehyde functional group, and then it is a polyol--it has several hydroxyl groups.0150

    And this isomer that I have shown here is D-glucose, and if you imagine the mirror image of this, you would have the exact same relative relationship; it would just be the mirror image.0160

    Nature typically prepares only a single enantiomer of any chiral molecule, and so sugars are an example of that.0175

    The ones that are naturally occurring are described as D-sugars, and the way we identify a D-sugar is: if we draw a Fischer projection (like this, where the most highly oxidized carbon is up top, and we draw all our chiral centers going down), if we look at the very last chiral center, if this OH is on the right, as shown, then that is a naturally occurring sugar; we are going to call it a D-sugar.0185

    Now, that D--the opposite...the enantiomer...if we were to draw the mirror image of this, that would put all of the OH's in the opposite position, including this last one on the left; that one would be described as the L-sugar.0211

    It's a capital L; it is actually a small capital L.0227

    That is different from the lowercase d and l we have seen for stereochemistry: remember, when we talked about optical activity, we described the optical rotation.0230

    It could be a + or a -α, and those that were +α we described as dextrorotatory, and the -α is levorotatory.0239

    That little d and little l just depend on the molecular structure; we have to measure those; we can't predict those; and those have nothing to do with the designation of d and l that we are going to use for sugars and amino acids.0248

    Make sure that you keep in note--"Not the same as d and l"--little d and little l.0261

    This is D-glucose, and D-glucose can exist in the straight-chain conformation, but actually, in solution (in blood and at that pH), it actually forms a ring; it prefers to exist in a cyclic form.0271

    And we are going to form a 6-membered ring (remember, 6-membered rings are very easy to form, because they have no ring strain).0290

    And so, the way it can form a ring is...what we have here is a carbonyl carbon; the reactivity of a carbonyl is going to be electrophilic--there is a partial positive on that carbon to make it electrophilic.0296

    And we have, with all of these OH's, a variety of nucleophiles; so if we look, 1, 2, 3, 4, 5, 6 atoms away we have a potential nucleophile.0308

    I'm actually going to take this OH on the last chiral center; and if we bring that up and form a ring, we are going to form a 6-membered ring.0324

    Now, we know that 6-membered rings prefer to take the chair conformation, so we are going to draw our chair that way.0333

    And, if we always draw our chair with this general shape--so we start with a zigzag up and go down--and we always put the oxygen in this top right corner; if we always draw our sugar, our 6-membered ring, in the same way, then it is going to be very easy to draw a glucose, because all of the OH groups are in equatorial positions; so it is a very stable molecule.0340

    And if we number our carbons, this is the carbon that got attacked--that is carbon 1--and this is 2 (it had an OH); 3 had an OH; 4 had an OH; and then, 5 has this oxygen, and then it has, also, a CH2OH.0372

    This is carbon 5, and up here, we have a CH2OH; so all of the substituents in glucose are equatorial--that means they are pretty easy to identify, or draw if you need to.0388

    Now, let's think about on carbon 1...carbon 1 used to be the carbonyl; it is now a single bond oxygen, which is going to get protonated, and we are going to have an OH here.0401

    And I am going to draw this...when you think about the stereochemistry of this OH, this is forming a new chiral center; so it's not fixed--you can either draw the OH in the equatorial position, or you could draw it in the axial position.0409

    I'm going to draw it as a wiggle line, and that means we can get a mixed stereochemistry; we'll look at that stereochemistry in just a bit, on the next slide.0422

    And another thing I want to point out about this cyclic form of the sugar is that this carbon--this is a very special carbon; it is described as the anomeric carbon.0434

    And that is the carbon that used to be the carbonyl; notice, the carbonyl has two bonds to oxygen.0447

    Well, even in the cyclic form, it still has two bonds to oxygen: here is one bond, and here is the other bond--2 bonds to oxygen.0453

    That is going to make it very special and unique, and it is going to be something we can pick out of any cyclic sugar--this anomeric carbon.0463

    There is special reactivity that is associated with this anomeric carbon we are going to be seeing.0473

    And, if we ever need to correlate that with the straight-chain form, we know that that anomeric carbon that is numbered 1 here corresponds to the carbonyl carbon.0477

    That is either an aldehyde or some sugar that is a ketone; there are aldoses and ketoses, depending on what the carbonyl is like; but glucose has an aldehyde here.0487

    OK, so let's take a look at where the OH is: we have different names for the sugars--different stereochemistry.0496

    These are the 6-membered rings of glucose; if the OH is on the anomeric carbon--so I can find that anomeric carbon...0504

    Now again, just because I usually draw it in the same general reference--it is the furthest-right carbon, but no matter how it is drawn, I see that this is the carbon with two C-O bonds.0512

    There is my anomeric carbon on each structure.0522

    And if the OH is pointing in the down position, we describe that as the α stereoisomer; so that means the anomeric OH is down, meaning it is in axial position.0527

    And, if the OH is pointing up, we call that β: the anomeric is pointing up, and this is in the equatorial position.0549

    OK, so when it's in a 6-membered ring, we no longer just call it glucose: we call it glucopyranose; a pyranose means it's a 6-membered ring--like pyran is a structure with a 6-membered ring.0568

    The full name for this molecule would be α-D-glucopyranose; and this is β-D-glucopyranose; and both of these exist--both of them are formed--when glucose cyclizes, and both of these exist in blood.0586

    Now, when it's a cyclic form, how can we tell whether it's a D-sugar or an L-sugar (the naturally-occurring sugar)?0602

    Well, for the 6-membered ring, we are going to have--this is the last chiral carbon, the last chiral center; that is the one that can show us whether we are looking at a D-sugar or an L-sugar.0608

    And so, again, when we always draw this same cyclo chair backbone of the 6-membered ring (it's not cyclohexane, because we have an oxygen in there), when we always have that same backbone, then having the CH2OH group up--that tells us that it is the D, the naturally-occurring.0620

    Now, we usually don't see any of the L-sugars, but if you ever need to distinguish between them, or if that is part of the assignment (to pick out the L-sugar), this is where we would look.0647

    The last carbon, the CH2OH, is up, so that means it is the D enantiomer that we are looking at.0655

    OK, very good.0662

    Now, glucose can also exist in a 5-membered ring, instead of a 6-membered ring: so here is 1, 2, 3, 4; if we stop at this oxygen, that is also a nucleophile that is in a proper position to attack the electrophile.0665

    And remember, 5-membered rings are reasonable to form, just like 6-membered rings; and so, what would that look like?--the oxygen attacks the carbonyl, and then we would form a 5-membered ring with an oxygen in there.0683

    And if we keep this carbon as carbon 1 on the right...now again, that carbon will have an OH, but it is of a mixed stereochemistry, so that OH can be pointing up or down.0699

    And then, we have the OH's; I don't have my stereochemistry right--I didn't draw these down.0711

    We draw this kind of like a 5-membered ring that is pointing out towards us; we are looking at it from the side, so each of these positions, you could draw the position as up or down.0719

    So, if we tilt this molecule on its side, we see this first OH is down, and the second OH is up, and the next OH we rotated around, and so I think it's pointing up here.0733

    I think this is the structure; I have it written out on the next slide, so we will see for sure.0748

    So anyway, we can form a 5-membered ring here.0752

    And we will check our stereochemistry.0755

    So, these are the two examples; and I think I just about had it right; so the place where we can have some variability in the structure and still have it be glucose (these are still glucose molecules)--now we call it glucofuranose, like a furan ring is a 5-membered ring.0757

    And, if we look at that anomeric carbon--anomeric used to be the carbonyl, and now has two separate bonds to oxygen--once again, we use the same terminology, the α position, because our OH on the anomeric carbon is down.0781

    And β is how we describe it when the OH is pointing up.0802

    OK, so we don't use the words axial and equatorial--that makes sense here, because it is not a 6-membered ring; but we just look for up or down to describe that.0808

    And that up or down--that α and the β--is related to the fact that this is the D-sugar; so going back to that 6-membered ring, assuming it's the D-sugar and that the CH2OH is up, then α is also up.0817

    So, it is actually describing its relationship to that CH2OH; so the α and β won't have the same connotation otherwise.0830

    OK, now let's see if we can try a mechanism, putting our organic chemistry hats on.0844

    Let's see if we can come up with a mechanism to show how we can maybe go from a 6-membered ring to a 5-membered ring.0848

    Now, what I did was: I simplified this problem by taking out all of the dashes and wedges; so I haven't shown the stereochemistry of all of these chirality centers.0854

    Glucose has a certain stereochemistry for each of its chiral centers; if you change any of those locations of the OH groups, it is no longer glucose--it's maybe galactose or raffinose or some other sugar.0864

    There are lots and lots of sugars.0876

    So, I don't know which sugar we are looking at, but we have a 6-carbon sugar, and we are going from a 6-membered ring to a 5-membered ring.0878

    OK, so how do we convert those two?0886

    The first thing you want to do is...remember, these are coming from the same sugar, the same acyclic sugar; so let's try and identify the carbon chain that is going to be common to both.0891

    Now, remember, they both started with a carbonyl; that carbonyl carbon had 2 C-O bonds; that carbon, even in the cyclic form, still has two C-O bonds; so the key here is: let's identify the anomeric carbon, and that is going to help us track the rest of the carbon chain.0900

    On this first structure, we look around: every carbon has just one bond, one bond, one bond, and then we find that this is the carbon that has 2 C-O bonds; so let's call that carbon #1, and we'll label it "anomeric carbon," just so we are clear on that.0916

    And then, let's find that over here: one carbon, one carbon, one carbon; the carbon-oxygen bond is what I'm counting--there is our carbon that has 2 C-O bonds.0936

    So again, this is our anomeric carbon.0947

    What is great about that--we could label that 1, and then we can follow our carbon chain, right?--this is not our carbon chain; this is our carbon chain: 1, 2, 3, 4, 5, 6; and over here, we have 1, 2, 3, 4, 5, 6.0952

    We know where all our carbons are as we track them; and what is going to be happening here is: we are going to be taking the cyclic structure, and we are going to be opening up the ring to go back to an acyclic structure, and then reclosing it, using a different oxygen, to form a 5-membered ring instead of a 6-membered ring.0970

    How do we open up that ring--what is the bond that we are breaking?--it is this anomeric carbon that needs to go back to being a carbonyl.0990

    This is the bond that we are going to be breaking--this oxygen on the carbon chain is going to go back to being just an OH group.0998

    What does our mechanism look like?--well, let's assume we have an acid catalyst; so our first step must be to protonate somewhere.1007

    I can protonate any of these oxygens--any of these oxygens can and will be protonated.1015

    But, if I protonate the oxygen that I want to leave, when that one gets protonated, let's take a look at the structure that we end up with.1020

    OK, lots of OH's; you can see why ignoring our stereochemistry helps us out a little bit.1034

    And now, we have protonated; OK, now, what did we make?--by protonating this oxygen, we have made an intermediate that is tetrahedral.1042

    There is a hydrogen here: it has 4 groups--2 groups have lone pairs; one of the groups has a charge; does this intermediate look familiar?1056

    What if I called it a charged tetrahedral intermediate?1064

    A CTI is something where bells and whistles (ding, ding, ding!) went off, because we said, "Hey, I know that structure!--this is something that can be unstable."1070

    And, in fact, what can a CTI do?--it can collapse, and that means the leaving group leaves, but the leaving group leaves with assistance from the other group; so this lone pair kicks down, and this bond breaks, and that group gets kicked out.1077

    And what we end up with, now, is...and there was a hydrogen here; you can add that in, because usually we draw our aldehydes with a hydrogen there...so this, now, has a carbonyl; that is carbon 1.1094

    And then, we can number our carbons again: this is 1, 2, 3, 4, 5, 6; keep track of them--that is good.1111

    And then, I don't know where the stereochemistry is; so we could just draw them--it doesn't really matter.1120

    But carbon 2 has an OH; carbon 3 has an OH; carbon 4 has an OH; carbon 5--what does carbon 5 have?--it now also has an OH, and then a CH2OH.1127

    OK, now I have drawn a Fischer projection, which now implies a stereochemistry; but let's just make a little note that we can ignore the stereochemistry; there is nothing special--I just wanted to draw this out of the straight chain.1143

    OK, and then, how could we then form this into a 5-membered ring?1157

    We have a protonated carbonyl that looks like a great electrophile, and if we go 1, 2, 3, 4, 5, then if this oxygen is our nucleophile, if this attacks the carbonyl, then that is going to close up and form a 5-membered ring.1163

    Let's take a look at where that brings us: I'll draw it with this orientation.1183

    I know I formed a 5-membered ring with an oxygen, so all I have to do is draw that tetrahydrofuran ring.1189

    And let's relate it to the structure that we are already given; so let's call this carbon #1; #1 has an OH (σ bond OH now); carbon 2 has an OH; carbon 3 has an OH; carbon 4 has this oxygen, which was an OH; it is still an OH, so that looks like an O+; and then, that oxygen just formed this bond to 1 and formed this bond to 1.1198

    That was our new bond.1230

    OK, so you can see that this was the new bond that was formed; we broke one bond, and then we formed a different bond.1232

    And what else is on carbon 4?--carbon 4 has a carbon with an OH, and then CH2OH.1238

    OK, so we have formed our bond, but we have one more step to do, because we attacked with a neutral alcohol; and so, this is now positively charged OH, and so, we just need to deprotonate as our final step.1255

    So, just like we used HA in the first step, we get that HA back in our last step; so this is just catalytic--all we need is a catalytic amount of HA to get this mechanism going; and then we are done.1269

    OK, so looking at sugars as organic molecules--as aldehydes reacting with alcohols--we know how to do carbonyl chemistry; we can do those mechanisms.1282

    Now, it turns out that sugars are actually building blocks that nature uses; they are also building blocks that synthetic chemists can use.1295

    They represent wonderful starting materials, because they are provided by nature with chiral centers intact.1305

    So, if you want to generate a chiral target molecule or a chiral drug target, let's say, a sugar is a great starting point, because you already have a certain number of chiral centers that are already set for you.1312

    OK, so let's look at some of the reactions that sugars can undergo; and this is going to set the stage for some of the reactions we'll see down the line.1325

    OK, so one thing we can do with glucose or any other sugar is: we can form an acetal.1332

    The way we form an acetal is: we react the sugar with an alcohol and some acid catalyst.1338

    OK, now, notice: when you do this reaction, the only product we get--the only methoxy group that gets added in--is at the...which carbon?--at the anomeric carbon.1347

    So, it is the anomeric carbon that has that special reactivity; none of these other alcohols react.1359

    These are just plain old alcohols, but this is not a plain old alcohol; this OH is on the same carbon as an O-R, and we have a name for a functional group when we have an OH and an O-R: we call that a hemiacetal--the word that is right there--a hemiacetal.1364

    So, sugars in the cyclic form are hemiacetals; normally we wouldn't form a hemiacetal, because they are not very stable, but in the cyclic form they are, and cyclic sugars--this is the one example where we are going to see them.1384

    OK, so what happens with a hemiacetal when you treat it with some more alcohol and acid--what is going to form is: we are going to replace this OH with another O-R.1397

    And what do we call it when a carbon has 2 O-R groups on it, 2 alkoxy groups on it?--we call it an acetal.1411

    A cyclic sugar is a hemiacetal; a reaction with an alcohol converts it to an acetal.1419

    Now, this bond that we make to the anomeric carbon--this is known as a glycosidic...it is called a glycosidic bond.1427

    This compound is now called methyl α-D-glucoside.1437

    OK, so methyl, because we added on a methyl group here; α--what does α tell us?--it tells us the stereochemistry at the anomeric carbon, and here we have the oxygen that is pointing down--that is the α stereochemistry.1442

    D means it is the naturally occurring sugar, and I could see that because the CH2OH is pointing up, like we know for the glucose.1459

    Gluco, because we are dealing with glucose; I can tell that because all of these groups are in the equatorial position.1468

    And then , the glucoside means that I have formed this glycosidic bond; so that means there is something now attached at that anomeric carbon.1474

    And this is the bond that we can form, that sugars can form, and that is a way of linking one sugar molecule to another sugar molecule.1489

    So, if we strip this away--let's say we wanted to do the mechanism for this; again, we are organic chemists, so this is not just magic that happens; this is something we can provide a mechanism for.1497

    To do the mechanism, let's just strip away all of this extra stuff, all the functional groups that are not involved in the mechanism, and go down to the bare bones; so this is what we have.1510

    Here is the structure of a hemiacetal: cyclic 6-membered ring with...the carbon that has the oxygen has another OH.1518

    OK, I don't care about any of the OH's that are just plain alcohols: alcohols don't react with alcohols--there is no reaction there.1529

    OK, but here is the hemiacetal with our anomeric carbon, and we are getting a substitution taking place with that anomeric carbon where the OH is getting replaced with an OCH3.1536

    We are going from a hemiacetal to an acetal.1546

    So, let's see if we can do the mechanism for that.1548

    OK, how do we form this glycosidic bond?--well, again, let's assume we had some acid catalyst, which we will just represent with HA.1552

    And, if we want to replace this leaving group, that would be a good place to protonate, because that is going to make it a better leaving group.1560

    So, our first step is going to be to protonate.1566

    OK, what does that do for us--why is that good to protonate?--because now we have a very good leaving group.1575

    What would it be if it were to leave?--it would just be a molecule of water; you don't get a more stable leaving group than water.1582

    OK, so we just made a good leaving group, and we have a nucleophile; now, how is that going to come in--how is it going to replace?1589

    SN1 means the leaving group just leaves--just ordinarily, you get a random carbocation and the leaving group, and the nucleophile comes in.1597

    Back side attack can happen: back side attack means that my methanol would kick out the leaving group; but this isn't a very strong nucleophile, so back side attack doesn't look very good.1606

    Well, in fact, neither of those mechanisms happens because this is not just an ordinary leaving group on an ordinary carbon; it's a leaving group on the anomeric carbon.1615

    So, this is not just a random leaving group; what I have here as an intermediate is a charged tetrahedral intermediate.1623

    OK, so when you have a CTI, it is now carbonyl chemistry; this is not an ordinary SN1 or an ordinary SN2; what happens is: the leaving group leaves with assistance from this leaving group.1630

    That is why the reaction happens here and not at any of the other OH's that are on the carbon chain.1645

    OK, if it was just a plain old SN1 or SN2, you could react anywhere you want; but no, what makes this special is: protonating at this oxygen gives a CTI.1653

    And how does the CTI kick out its leaving group?--we use two arrows; it collapses.1663

    It collapses; we get a resonance-stabilized carbocation intermediate.1668

    OK, so by using two arrows to collapse your CTI...collapse the CTI, and we just kicked out our molecule of water...now we see the carbonyl.1674

    We see that this is, in fact, carbonyl chemistry; our anomeric carbon goes back to being a carbonyl.1686

    This is now a great electrophile; it is like a protonated carbonyl; and so now, hopefully, you can see how our nucleophile, the methanol, can get involved.1691

    The methanol will attack at the carbonyl carbon and break the π bond.1702

    So now, this oxygen has its lone pairs back, and how about this oxygen?--it has a methyl, has a hydrogen, one lone pair--so that is now my O+.1711

    This is part of the mechanism that is used; go back and review your mechanism formation of an acetal; part of the mechanism--we are kind of looking at the last part of the mechanism, where we have gotten to the hemiacetal, and now we are kicking out that water, and we are bringing in the second molecule of the alcohol.1723

    Here we already have one of the O-R groups in place, so we are just adding in the other O-R.1740

    OK, and all we have to do is deprotonate, so I can use my A- that I formed in the first step.1745

    So again, this is catalytic, just like any acetal formation; catalytic and acid, and we are done.1749

    OK, so what is important is that we recognize that the anomeric carbon of a carbohydrate is a special one, and substitutions can occur at that position very readily, because that other oxygen can help forcing out the leaving group.1759

    This is the way that we can form sugar chains; if we just bring two sugar units together, we can form a disaccharide, meaning there is a 2-sugar unit.1775

    So, if we bring together glucose (that is the blood sugar that we have been working with) and--this one is called fructose (again, both the naturally occurring fructose is...you may have heard of that: that is the sugar that is in fruit, that makes it naturally sweet)...so if we bring these two together, instead of just methanol coming in and replacing...this is the OH that is going to be leaving; there is our leaving group.1785

    And who is the nucleophile?--well, we can see that it is the other OH, so actually, one of these is the leaving group or the nucleophile (we can kind of think of it either way--leaving group/nucleophile)--the point is: one of those OH's is getting kicked out, and the other oxygen is coming back in.1811

    And they are both happening at the anomeric carbon, and so, that is where we can get our reaction to take place.1829

    We lose water in this reaction; we eliminate a molecule of water, so it's a condensation reaction; and we end up with this disaccharide; and when you mix one molecule of glucose with one molecule of fructose, we know this as sucrose.1838

    And sucrose is what we use as table sugar; so this is what we take spoonsful and put on our cereal, or in our coffee, or we use in baking: this is the sugar we use in our cooking as a sweetening agent.1856

    And so, we took our fruit sugar and blood sugar components to make that.1870

    So of course, when we consume this as something in our diet, then this is going to be cleaved, and it is going to yield, again, a molecule of glucose and a molecule of fructose.1874

    That is why sucrose--taking in table sugar--has a significant impact on our glucose levels.1886

    Now, we can use this same idea and form polysaccharides, meaning we are forming long carbon chains.1894

    And so, this first example we will look at is starch; now, starch--there are a couple different versions of this.1902

    Amylose is an unbranched version, so we just kind of get a long chain; amylopectin is a highly-branched version; so here we are showing a branched version, because here we have a chain of glucose units, and then it is chained off this way.1910

    So, when you take a look at a glucose unit, what has happened is: we have formed a bond to the anomeric carbon (OK, that is always where we are going to be attaching some new nucleophile).1922

    And so, here we have attached it to this OH at the far left on the molecule.1934

    Now, these glycosidic bonds are described as α-1,4-glycosidic bonds; so we see the α that describes the position of the group that has been attached to the anomeric carbon (it is in the down position).1942

    These are all α connections; OK, and it's a 1,4 glycosidic bond--it has gone from carbon 1, the anomeric carbon of one sugar, to 1, 2, 3, 4...the carbon 4 of another sugar.1960

    So, it is just called an α-1,4-glycosidic bond.1977

    And we can have some cross-branching by introducing, every once in a while...this central glucose unit--this OH, added on to another glucose, and this OH also did; and so now we get a branching point.1981

    And so, that is what we get for these different structures.1996

    The nature of these starch molecules is that they are water soluble; look at all the OH's--we have a very polar structure, so it loves water; it is water-soluble.2001

    It is digested by animals, so this is the starch that we have in our diets; we can have it in potatoes and rice and bread--those kinds of things that we describe as high-starch items...corn.2012

    We also use them as thickening agents, like cornstarch is something you could add to gravy or sauces to make it thicker.2025

    And so, we have this polymer structure that can go in there and kind of act as a thickening agent.2032

    Now, a different polysaccharide is cellulose; now, notice the structure of cellulose: it kind of has this long, very linear chain; and the difference here is that now we have a β-1,4-glycosidic bond.2038

    So, they are still glucose units; they are still being connected at carbon 1 (let's go this way) of one and 1, 2, 3, 4 of the other; notice that every other glucose unit has been flipped over, so we can actually see the structure of it.2053

    So, this is carbon 1, 2, 3, 4; so we are connecting at the 4 position and at the 1 position.2075

    It is still a 1,4 glycosidic bond, but now each of the anomeric carbons is in the β position.2082

    OK, and so, it is tough because it is upside down; but it is in the equatorial position, right?--that is what we have, the β position.2091

    Now, because this is a linear structure, that means it packs very tightly, and it ends up giving a rigid structure that is not soluble, because these pack so tightly, they want to stay with each other; they don't want to be surrounded by water molecules and disrupt those.2099

    This is what is used in...is cellulose; these are cell walls; this is what nature uses in plant fibers to make rigid structures, and these are not digestible by most animals, and humans.2115

    We can't eat wood or twigs and leaves--those kinds of things; and when we eat leaves, like lettuce or vegetables, the cellulose is something that passes through as insoluble fiber; so this is something that you can't digest.2130

    So, little differences in structure really give big differences in their properties.2143

    And we have some other sugar-containing biomolecules, now that we know what a sugar looks like, and we know how they can react.2152

    Here is an example of a ribose sugar: ribose is a 5-carbon sugar that is very common.2164

    And it is linked with another molecule, with a nucleophile; here is our anomeric carbon: now, instead of two oxygens, we have an oxygen and a nitrogen.2174

    But again, you can imagine that we can break this back off and open up the ring and come back to a carbonyl.2186

    This is still our anomeric carbon; it has the same oxidation state as a carbonyl, and that is the carbonyl part of our sugar.2193

    But now, in this case, instead of having another oxygen come in as a nucleophile, we have one of these--we have a base that is added in, a nitrogen group.2200

    And so, a base can add in, and we describe this, then, as a ribonucleoside.2210

    Now, ribonucleosides are what nature uses to build RNA.2215

    And over here, notice that we have lost one of the OH's that ribose naturally has; so this is now called a deoxyribonucleoside.2219

    We have lost our oxygen; and deoxyribonucleosides are the building blocks for DNA.2231

    We will find that sugars are an integral part of both RNA and DNA structures; we are going to see those shortly, and now we can see that sugar portion of the structure and where that comes from.2236

    OK, next let's talk about amino acids and proteins: these definitely have a lot of functional groups that we are familiar with, and a lot of reactions that we are familiar with.2254

    When we say amino acids, naturally occurring amino acids, we are typically referring to α amino acids.2262

    That means we have a carboxylic acid, and on the α carbon, we have an amino group.2270

    So, if we just say "amino acids," we are typically referring to α amino acids.2276

    And amino acids are the building blocks to form proteins; so amino acids link together to form long polymers known as proteins.2281

    If we take a look at their structure, their stereochemistry--so first of all, I have shown an example of an amino acid; if it is drawn this way, the side chain--this R group represents a side chain--it can be just hydrogen; one of the amino acids just has hydrogen here.2290

    But we have a wide variety of groups that we can attach in this R position, and that is what gives us our different structures of amino acids, and kind of the building blocks to make different types of proteins.2310

    There are about 20 naturally occurring amino acids, and that is kind of what we use as our alphabet to build all of these different words and sentences that we have as proteins.2322

    This is an L-amino acid; L is the one that nature makes naturally.2333

    The terms D and L are kind of historic on where those terms come from; so you don't necessarily need to know the background for that; but this is what the L form looks like.2341

    The enantiomer, of course, would be the unnatural one--the one that we would have to make synthetically.2353

    And, if we look at the stereochemistry here, if we were to look at that chiral center and assign it as an R or an S, it depends on what this R group is, of course, but almost all R groups...our #1 priority group is this nitrogen, because we are comparing nitrogen, carbon, and then this is usually carbon, and then a hydrogen.2361

    So, this is usually 1; this is usually #2; this is usually #3; and the hydrogen is a dash; so if we go 1, 2, 3, what do we get there?--it looks like, counterclockwise, this is the S configuration.2385

    And that is true for all amino acids except cystine: cystine--the R group is an SH, and this sulfur is a higher priority than this oxygen.2402

    Because of that, those two, when we do the nomenclature--the position of 2 and 3 changes, and so we get the R configuration.2420

    OK, so most naturally-occurring amino acids have the S configuration when we draw them out; you can draw them this way or this way or flip them up and down.2427

    So sometimes the side chain is a wedge or a dash, depending on if I took this amino acid and just flipped it over; suddenly, it would still be naturally-occurring, but it would be a dash.2435

    They are kind of drawn different ways each time.2445

    But what is interesting about it is: we have a carboxylic acid functional group, which is, of course, acidic--readily loses its proton here to give a resonance-stabilized anion, carboxylate.2448

    And we have an amine; that is why they are called amino acids.2465

    And we have an amine: now, carboxylic acids are acidic, and amines are basic; that means amines readily accept protons.2470

    And so, the acid-base characteristics of amino acids and some of their side chains is really significant when we are looking at the structures of amino acids and proteins and so on.2481

    And, in fact, if we look at a neutral pH like we would have in the blood (blood is not quite 7, but if we had something around 7), this carboxylic acid is acidic enough and this is basic enough that we will observe a proton transfer.2492

    And so, instead of being written in the neutral form, really, amino acids should be written (if we are considering ones in solution and a physiological pH)...they should be drawn as a zwitterion.2511

    A zwitterion means there is a + and a -.2527

    So, you can always pick out an organic chemist when they go to draw an amino acid, because we just draw these nice neutral structures; but in almost every biochemistry textbook or biochemistry chapter, you are going to see it drawn as this.2530

    That is really how it is: it is an N+ and an O-.2544

    This arrangement is more stable--it is more stable to have an N+ than to have the proton on this oxygen; it shows you just how acidic a carboxylic acid is, and how basic an amine is.2547

    They are strong enough to react with one another.2561

    OK, so that is the way we are going to draw amino acids.2563

    Now, how do two amino acids come together to link together and eventually continue linking to make a polymer, to make a protein?2567

    Well, it's a condensation reaction, and what happens is: the nitrogen of one amino acid acts as a nucleophile, and the carbonyl (right?--this is partially positive) of another acts as the electrophile.2576

    And that is the reaction that we are going to have happen: so the nitrogen is going to come in and attack the carbonyl; it's going to do addition; it's going to do elimination.2593

    I'm not going to show a complete mechanism here, but this is going to be our leaving group, and we are also going to lose one of these hydrogens; so the result (and again, I'm just going to leave the NH2 and the OH as neutral to make this discussion a little easier) is: we are going to form a (let me draw it up this way; we just kind of ended up flipping it over again--they end up getting flipped if we're drawing zigzags)...2602

    This nitrogen has added into this carbonyl, and what functional group did we make?--we now have a carbonyl with a nitrogen group attached; this is called an amide.2634

    We just formed an amide bond; and that is the key linkage that we have for proteins: we take the amine of one and the carboxylic acid of the other, and we make an amide.2646

    We link all of these together as a polyamide.2657

    And it is called a condensation reaction because, at the same time, we just lost a molecule of...what did we just lose here?--we lose this OH and this H; we lose a molecule of water.2662

    We have amides when we are looking at proteins; amides are very stable functional groups; they are quite unreactive; so that means we can have all of these proteins that are pretty...can reliably resist hydrolysis and be quite stable, because the amide is such an unreactive functional group.2675

    Now, another thing that is interesting--we call this the peptide bond; this amide bond that I just described is also called the peptide bond; and when we think about the stereochemistry, the conformations, the shape of a protein, an important part of that understanding is recognizing that what makes amides so stable is: there is resonance stabilization.2696

    The nitrogen is very, very good at sharing its lone pair with the carbonyl.2721

    And so, if we draw this resonance form, we have an O- now, and an N+.2726

    OK, we have this resonance form; now think about resonance: remember, when we have resonance, that means it's not sometimes this and sometimes this; it is not an equilibrium.2746

    It is not an equilibrium between these two structures; it means that the actual structure of the peptide bond, of this amide, is a blend--is a hybrid of those.2757

    So, when we think about the hybridization of this nitrogen, it must be...if it's sp2 here, it must have been sp2 here as well.2767

    Remember, resonance does not involve changes in bond angles or bond lengths--all of the atoms are frozen: we are just moving non-bonded and π electrons around; we are just moving electrons around in p orbitals.2779

    OK, so that means the structure of this...and, of course, the carbonyl carbon is sp2 hybridized, still sp2 hybridized.2794

    So, what we have is a trigonal planar nitrogen, trigonal planar carbon; so these four atoms, this nitrogen, this α carbon, these three atoms and these three atoms, are all coplanar.2801

    And so, what we have is like a little rectangle here.2817

    And so, we can rotate in this position; we can rotate until, if this was another amide, that would be another planar chunk.2821

    So you have these planes--these amide planar portions, and they can rotate, and then they will do that to have favorable interactions and so on.2830

    When you are getting into protein structure, it is very important to realize the planarity of this amide bond, this peptide bond.2839

    And an understanding of that comes from your foundations in organic chemistry, understanding resonance, understanding the stability of the amide, and in knowing how good the nitrogen is at donating its electron density.2849

    In other words, it has a lot of this character--when you look at the hybrid, a lot of this character; and it's planar.2861

    OK, so what are we going to do with proteins--how are those interesting to us?2870

    Well, proteins are everything in the body: proteins are the work horse; they are what make all of the reactions happen.2873

    They can be used as building blocks, as building materials.2884

    Proteins are long polymers, so depending on their structure, they can be rigid; they can have strength; so when you look at the structure of muscles...2889

    Now, this is something--growing up, when I learned about proteins, I knew that proteins--that amino acids built up proteins, and proteins are one of the things that we eat, and that one way you can get that is from meat, which is the muscle of animals.2899

    So, I always knew that one thing you can build from proteins are muscles.2916

    OK, but that is not the only thing: if you look at the structure of your skin, and rigid things like your bones, your hair, your nails, the material that makes your fingernails--those are all protein structures, as well.2922

    So, we need proteins to build our bodies, to build all the different components of our body that make us be able to not just fall apart like a big mass of jelly.2936

    They also act as enzymes in the reaction: an enzyme is something that catalyzes reactions.2951

    If you think about all of the reactions that are going on in our body, that allow us to function--if you think about metabolism (you eat something and it gets broken down into various components and generates energy and so on), every one of those reactions is going to be catalyzed by something that allows the reaction to happen.2958

    And it is going to be some kind of enzyme; so enzymes are the things that let the reactions happen.2980

    We can have antibodies; so if you are sick, if you have something foreign coming in and your body needs to attack it, proteins are used to mount that defense.2985

    It also helps in communication in your body, or transport; the hormones we have in our body, that monitor all of our levels; haemoglobin--the structure of haemoglobin (that is what transports the oxygen around our body in our red blood cells)--that is a protein, as well.2998

    Proteins really get things done; in fact, they even do gene regulation.3017

    Proteins are made from DNA, and the way that you turn on that DNA production or slow it down is: other proteins come in to do the signaling.3026

    So, you could have signaling; you could have transportation; you could have structure--just a huge variety of actions that come from proteins.3037

    They are really an incredibly important part of biochemistry.3045

    Now, what do the different amino acids look like?3052

    At some point, you will probably need to be familiar with these or memorize these and get to know them.3055

    We have certain amino acid side chains that are nonpolar; so we could just have a methyl group that is alanine; the isopropyl group is valine, I think--I really don't know my amino acids, so forgive me.3061

    We can have some that are polar; so this one has an OH group; this one has an amide group on it; so we have some polar ones.3075

    We have others that might be acidic themselves, so remember, these are attached to the amino acid; so all proteins have our one carboxylic acid and our one amino group.3083

    In addition, part of the side chain, there can be a second carboxylic acid--something that is acidic--or maybe a phenol.3094

    This is a carboxylic acid, so we know those are acidic; this is a phenol--phenols are also acidic.3101

    It is very easy to lose this OH, because the resulting O-, the phenoxide, is resonance-stabilized; so phenols are acidic.3109

    And we can also have functional groups that are basic; so again, in addition to the amine of the amino acid, you can have a second amine, and that could also serve as a base--and other rings, as well--other nitrogens.3116

    OK, so our various side chains give different properties, because they have different reactivities, as well.3133

    And we have a table here--one of many--again, you can Google this; any textbook will have it--organic or biochemistry textbook.3143

    You can Google this, search online, find amino acid tables; and so, this is the one that just kind of shows...we have 21 amino acids being shown here.3152

    And again, they are kind of broken up into ones that have charged side chains; so when we have basic side chains, they can get protonated and have a positive charge.3161

    When we have acidic side chains, they can be deprotonated and have negative charges.3173

    We have ones that will never have a charge--you know, alcohols won't react; amides won't react with anything.3178

    And then, we have hydrophobic side chains--so just aromatic groups or alkyl groups, for example.3185

    And so, depending on the properties of the functional group, your proteins are going to fold differently, are going to have a different shape, where we try and put these hydrophobic groups together and get them away from a polar solvent like water, and so on.3195

    OK, so the actual structures of the amino acids are critical to their shape and their function.3215

    Now, another property that you can learn about for amino acids is their isoelectric point--that is the pH at which the amino acid is going to be neutral--it's going to be zwitterionic.3224

    It is still going to have charges, but overall, it is going to have a net charge of 0 for the majority of the molecules.3237

    And so, for example, this is glycene, so glycene looks like it is missing its R group, its side chain; but actually, it just has a side chain of hydrogen.3243

    Glycene is our simplest amino acid--it is not chiral, so this doesn't have D or L or R or S.3252

    And so, we can look up the pKas in various tables; the pKa of the carboxylic acid of glycene is 2.35; the pKa of the ammonia group, of the amino group...3261

    Now, when we say pKa, that is the tendency of something to donate a proton; so anytime we are talking about a pKa of an amine, we really mean the pKa of the ammonium group.3276

    OK, so we are going to look at the protonated form of that amine when it has a positive charge, and we are asking, "How likely is that to lose its proton to go back to the neutral form?"3290

    The pKa of a carboxylic acid starts at a neutral form and goes to an anion; the pKa of an amine starts at the protonated form and goes to the neutral structure.3300

    OK, so sometimes textbooks or tables are not very clear on that; but you just want to make sure that you recognize that pKa is for the amino group.3310

    These are kind of typical: acids are around 2; ammonium groups are around 10; and the pI is the pH at which it will be exactly neutral, or the majority of the molecules will be exactly neutral.3320

    It is an average of these two--that is how we get the pI.3336

    So, if you do 2.35+9.78, if you just take the mathematical average, we are going to get 6.06, approximately.3342

    That is a way that you can figure out the pI.3352

    When we look at a pH around...let's look at a pH of 6, just so we're a little more precise (it would be about the same at 7, but a pH at 6): when this is at the isoelectric point, then we know we are going to have the zwitterionic form.3357

    So, instead of the OH, this is...so pH of 6 means that my OH is going to be an O-, and my NH2 is going to be an NH3+.3375

    Now, we are back to the zwitterionic form that...I said at the beginning that amino acids at neutral pH (or more technically, at their pI) are going to be zwitterionic like this.3387

    OK, so what is going to happen, then, if I increase the pH?3402

    All right, that means it is more basic; so what do bases do?3408

    Bases deprotonate things; so what is going to happen is: we are no longer going to have this protonated.3413

    Remember, it has a pKa of 10, so as soon as we get above 10, we are going to deprotonate that.3421

    So, at a pH of 11, the majority of the molecules are going to have a net negative charge, net -1 charge.3430

    And what if we have a very acidic pH, like a pH of 1?3441

    Now, that means we have...anything that can be protonated will be, so you can think in base "anything that can be deprotonated will be," and at strongly acidic conditions "anything that can be protonated will be."3447

    The amino group is going to stay protonated, but the carboxylic acid group, if you come down below 2.35, is going to get reprotonated, and now we are going to have a net +1 charge.3459

    An amino acid can have a + charge; it can have a - charge; at the isoelectric point, it has a negative charge.3475

    Now, what if our side chain also has an acidic or basic functional group?3485

    OK, so for example, aspartic acid: we still have our amine; here is our amino acid; we still have the carboxylic acid and the amine group.3491

    We always have those two pKas of the carboxylic acid and the ammonium; but it has second carboxylic acid group, so it has a third pKa, and that has a pKa of 3.86.3502

    So again, pretty low--carboxylic acids are usually somewhere around 5 or so, or even lower, because we have a positively charged group here, so that makes it even more acidic.3518

    Now, how do we calculate the pI there--at what pH is this molecule going to, overall, have a net charge of 0?3531

    OK, well, what we do is: we take the two pKas that are closest in value, the two closest pKas--so this one is 2 and this one is about 4; those are much closer than this one out here at 9.8; so we are going to take those two closest pKas, and we are going to average those.3542

    If we take 3.86 and 2.10, and we divide that by 2, we get 2.98, either exactly or close enough.3561

    OK, so that is how we handle that; so in other words, we are asking, "When is this going to be neutral?"3571

    Well, it has two acidic functional groups; so we are going to kind of ignore this high pKa and assume, "Well, no matter what, the ammonium group is going to be positively charged."3577

    So, if the ammonium group is going to be positively charged, what we need to balance it out, to make it neutral, is: we need one negative charge.3591

    And the way that we get one negative charge when we have two carboxylic acid functional groups is: we find the pKa that is exactly between those, where now half the molecules are going to have a negative charge.3599

    And that will exactly average out to a -1 charge, instead of a -2 or a 0; it will average out to a -1; so our -1 cancels out the +1, and we have an overall neutral molecule: zwitterionic, but neutral.3610

    OK, histidine is another example with a side chain that changes charge--can be charged.3628

    Here is our amino acid; so this is the side chain now, and this group is what can be charged; it's this nitrogen here...I'm sorry, this nitrogen here--that can be basic, that can be protonated.3639

    And so, it has a pKa of 6.10; now again, you might look at that and say, "Oh, that must be this hydrogen; we can deprotonate that hydrogen," but no: we are not going to remove the hydrogen that we added.3654

    And amine works; its pKa is...it's the protonated version going back to the neutral nitrogen.3666

    We would never want to form an N-; that is highly unstable, very, very reactive; so it's either an N+ or a neutral nitrogen.3672

    And that has a pKa of 6.10.3679

    So, how do we calculate its pI?--we look at our three pKa numbers; we pick the two that are closest together; and we average those.3682

    9.18+6.10, and we divide by 2, and it gives us 7.64.3693

    So again, we think about it: we have these two basic side chains that can have positive charges or neutral; so when we are up at this pKa, the carboxylic acid is definitely going to be deprotonated.3701

    Remember, the carboxylic acid gets deprotonated right away; it has a really low pKa.3714

    So we already have one minus charge, one negative charge; so what we need to balance it out is one positive charge.3718

    The way we calculate that pH is: we say, "Well, if we're right in between these two pKas, then we'll have one that is neutral and one that is positive, on average."3725

    And so, we will have this +1 that cancels out the -1; we will have an overall neutral molecule; that is called the pI point, isoelectric point.3733

    A lot of the work that you do with amino acids and proteins in biochemistry is to do titrations and study, with the amount of titrant that you have added, the amount of base that you added, what is the pH of the solution.3742

    And so, from that, you can calculate what is the pKa of each functional group and things like what is the isoelectric point and so on.3761

    Those are some of the calculations that you have in store, if you are headed to biochemistry.3769

    This is a much more complicated case; let's ask, "What is the net charge?"--so this isn't so much an isoelectric point question--"What is the net charge of this tetrapeptide at pH of 6?"3776

    This, again, is a common type of question that you have, that you should be able to evaluate and assess: for each functional group that is either acidic or basic, what will its state be?3789

    Will it be in the protonated form, or will it be in the deprotonated form, based on the pH that is given?3803

    OK, so first of all, let's look at this: this is the first tetrapeptide we have seen; that means we have four amino acids.3811

    Let's start down here: here is our nitrogen, α carbon, carbonyl; so there is our peptide bond; there is our amide bond; there is one amino acid.3819

    This is glutamic acid.3828

    Now, nitrogen, α carbon, carbonyl--so there is our second peptide bond we could cleave, so this is arginine up here.3831

    And then, nitrogen, α carbon, carbonyl; there is our third peptide bond; this is cystine down here.3839

    And our final one is asparagine.3846

    OK, so those are our four amino acids; and what is given in parentheses are the pKas of side groups that could have a charge.3849

    OK, so asparagine does not have a pKa for the side chain, because this is an amide, and an amide has no reaction with acid or base; you are not going to protonate this amide.3861

    Remember, this nitrogen is resonance-stabilized, so it doesn't want to be protonated; you can't deprotonate it without super, super strong bases.3874

    So, this is a neutral...this is always going to be neutral.3883

    And it is polar, but it is not something that is going to act as an acid or a base.3889

    OK, cystine has a pKa of 8; so this is actually acidic; an SH group is quite acidic, because it's reasonably easy to remove that hydrogen, because an S- with that large surface area delocalizes that charge over a large surface area; so that is a fairly stable negative charge.3894

    That is somewhat acidic.3916

    OK, up here, this is called a guanidine functional group, and like most amines, it can be protonated; but rather than protonate down here, you could actually protonate this nitrogen (this is basic), because if I protonate here, you could have resonance stabilization to delocalize the charge.3919

    This is the basic part of this; it has a pKa of 12.3943

    And that means we could have a positive charge here, unless it's above pKa of 12.3947

    That is when it would get deprotonated.3956

    And then, finally, we have glutamic acid; glutamic acid has an extra carboxylic acid functional group here, so of course, that is acidic.3959

    We have all of these different groups; let's see how they are going to behave.3967

    We have a pKa of 6, so that is slightly acidic; but still, we are close enough to 7 where we can assume--because I didn't give the pKas for these terminal groups, but we could assume, like any amino acid--we can assume that this carboxylic acid is a carboxylate, and this amino group is an ammonium.3970

    So, we have an O- and an N+; we would expect that for those functional groups, any time we are in neutral pH.3997

    I should also mention that the way we draw the amino acid--here are the abbreviations for glutamic acid, arginine, cystine, and asparagine; those are the 3-letter abbreviations for those amino acids.4004

    And they are written out in this order--they are always written out in the order where this end has the nitrogen free; so this is described as the N-terminus (the N-terminal, the N-end--nitrogen end).4022

    And we follow along to the amide, and then at the end, we have a carboxylic acid, and that is where our carbon is; so we call this the C-terminus.4037

    We always have the N free amino group here, and then the N-group--that is the order in which we are writing it, so it's important, because it would be a different tetrapeptide if we had them in the opposite order.4047

    That is important: I could never keep this straight, and I always thought it would just be nice if this was alphabetical, that the carbon end came first and the nitrogen end came last, because then that would be alphabetical.4062

    But I guess, if you remember that it is not alphabetical--I guess it is just as easy to remember.4074

    So, we're always starting with our N-terminus, and then we hook up an amide and an amide and an amide, and we end up with our carboxylate group at the end.4077

    OK, so we will handle those; and then we look at our other functional groups, and here we have a carboxylic acid that has a pKa of 4.4085

    So, you would have to be below that peak--that pH would have to be below that in order to be protonated.4096

    Any pKa above that is basic, so we are going to deprotonate the carboxylate, just like we did over here.4102

    Carboxylic acid will be deprotonated.4110

    OK, how about cystine?--cystine has a pKa of 8, so a pH of 6 means it's a lower pH, so that is an acidic medium; so is that going to be deprotonated?--there is not going to be anything to deprotonate this; this will still be protonated until we get above pKa of 8.4114

    This will remain neutral; it remains protonated.4136

    OK, in this case, for cystine, protonated means neutral; sometimes we start out neutral; sometimes we start with the positive charge.4144

    OK, this functional group is called a thiol; an SH is called a thiol.4152

    A thiol remains protonated at a pH of 6.4158

    Amide, we said, is no reaction; so let's come back up to this guanidine functional group; this is basic, so this could have an N+; and a pH of 6...compared to pKa of 12, pH of 6 is much more acidic, so we have a good source of protons.4161

    So, I think this is going to be protonated; it wouldn't become deprotonated until a very, very basic pH above 12.4177

    Just like this free amine is protonated--you know what neutral pH is--then this guanidine is protonated, as well.4186

    It is even more basic than an amino group would be.4194

    OK, so we protonate each of those; so it looks like we have a + and a -, and we have a + and a -; and so, overall, what is our net charge?4199

    Our net charge is 0.4212

    It ends up being neutral at this pH, with the particular functional groups that we have.4215

    But in each case, you want to evaluate the amino acids separately and decide whether it's going to be negatively charged or neutral or positively charged.4220

    OK, the next biomolecule we are going to look at are the nucleosides and nucleotides that make up DNA and RNA.4234

    And the first thing we will look at are nucleic acids called ribonucleosides.4244

    Now, ribo- tells us that we have a 5-carbon sugar; so that is part of this; and it is called a nucleoside when we take that 5-carbon sugar (here is 1, 2, 3, 4, 5) and, at the anomeric carbon, we attach a base--some kind of nitrogen structure.4250

    And when we vary that base, we are going to get different ribonucleosides out.4275

    These are described as nucleic acids.4282

    And so, we have cytodine, which is abbreviated with the letter C; uradine for U; adenosine is A; and guanosine is G.4284

    These ribonucleosides, C and U and A and G, are components, building blocks, that we are going to have for RNA.4294

    Now, we call it a ribonucleotide, instead of a nucleoside, if on the 5' position, we add this phosphate group.4309

    We describe it as phosphorylated ribonucleoside; so we start with a ribonucleoside, which just had an OH here, and we add this phosphate group, and now we call it a ribonucleotide.4324

    So again, whatever base we have here, we could still have the A and the U and the G; but it's going to be called a nucleotide instead.4335

    Now, the purpose of that phosphate is: this is now going to act as a linker, so that we connect one of these ribonucleosides to another.4344

    We take these two ribonucleotides that have the phosphates on them, and same base, different base, whatever; and what we can do is: one of these oxygens at this position--at the 1, 2, 3 carbon--is going to add into the phosphorus and open up, and then collapse back down.4357

    And we are going to get a linkage going on here; and we have this phosphate linkage.4383

    This is the linker that we are going to use to connect the two sugars together.4391

    So, kind of like we had with our proteins--we had a carbon terminus and a nitrogen terminus (C terminus and N terminus)--the ribonucleic acid structure (RNA) has a directionality to it, as well.4397

    The end that has the free phosphate group we call the 5' end, because that is the linker that is on the 5 carbon; and the other end that has the free OH that is ready to attack another phosphorus group, and so on--we call that the 3' end.4417

    So, it's a 5' end to a 3' end; and we are going to continue adding nucleotides, one by one, and we make this long polymer.4435

    That polymer is called RNA, ribonucleic acid.4442

    Now, we also have deoxyribonucleic acids; those start...we can look at the structure of deoxyribonucleosides, and these are the same structures we saw before, except notice that we are missing one of our OH's.4448

    And so, this is no longer cytodine; it is deoxycytodine, deoxyadenosine, deoxyguanosine; so we still have C and A and G.4466

    Now, we used to have uracil here, but instead, we have thymine...I'm sorry, it was uradine; now this is thymadine; and the difference here is that we have added a methyl.4476

    So, if there is no CH3, then that is how we get the base that defines uradine; and here we have thymadine, and it's deoxythymadine, because there is no OH.4489

    The four bases that we have--the four nucleic acids we have that go into DNA--are C and T and A and G.4501

    They look a little different--the bases look a little different--for these two polymers.4511

    OK, now, but they can still come together with the phosphate linkages to make chains, just like we saw for RNA.4518

    Now, if you remember the structure of DNA--DNA has 2 of these strips, and they are linked together, and that is the helix that is going to be formed, the double-stranded helix.4525

    Two of these strands are going to come together, and the way that they come together is by hydrogen bonding.4541

    OK, and what is going to happen is: we are going to have one of the pyrimidine bases (so C or T--this 6-membered ring is described as a pyrimidine); it is going to link up with one of the purine bases (so this bicyclic base is called a purine).4546

    And so, I'm just focusing on the base part, so we still have the sugar part and then the phosphate, and so that is kind of the backbone.4562

    And what is going to happen is: when you have C and G lined up, we have the possibility for forming a hydrogen bond.4570

    We form hydrogen bonds between hydrogens that are either on nitrogen or oxygen; those hydrogens are special, because they are very, very partial positive.4578

    This NH bond is very polar--partial minus on the hydrogen, partial positive on that hydrogen; and so, that is going to interact; anything that has a lone pair of electrons can accept that hydrogen bond.4589

    We call this a hydrogen bond donor; any NH or OH group is a hydrogen bond donor, and anything with a lone pair is a hydrogen bond acceptor.4606

    And these structures are very nicely formed, because they are complementary in that we have a hydrogen bond donor lined up with a hydrogen bond acceptor, and then there is a second one we can form, because we have a lone pair here, and we have another NH.4623

    We can form a second hydrogen bond, and guess what: we have another NH and another carbonyl, and we can have a third hydrogen bond.4642

    So, these are just two molecules that fit together perfectly--very strong attraction to one another--and very reliably hold together.4650

    We get hydrogen bonding between these complementary base pairs.4658

    OK, the same thing can go on with the T and A bases; OK, but here we have just two hydrogen bonds that can form between this carbonyl and hydrogen, and between this nitrogen and hydrogen.4663

    OK, so in these cases, in DNA, they are all NH's that are the hydrogen bond donors; we don't have any alcohol groups--they are all NH's.4675

    The hydrogen bond acceptors are either carbonyls or nitrogens with a lone pair.4688

    What we end up with is this double-stranded structure; we have...here is the 3' end and the 5' end.4696

    Remember, the backbone is--we have a ribose sugar, a deoxyribose sugar if it's DNA--deoxyribose sugar, and then this phosphate linker that connects at the anomeric carbon.4705

    So, we have a sugar-phosphate backbone; we call it a sugar-phosphate backbone.4720

    And attached to each of those sugars is one of the bases--either A or T or G or C.4730

    And so, any time you have a C and an A and a T as the three bases in this portion of your DNA strand, then this is going to link up; it's going to be complemented by a G with three hydrogen bonds, and then a T with two hydrogen bonds, and another A with two hydrogen bonds.4738

    And it is going to line up antiparallel--we call this antiparallel, because the 5' end of one (where the phosphate end is) is going to link up with the 3' end of the other.4756

    We have the phosphate end on one end, and the phosphate end on a different end.4771

    OK, so this is the double-stranded structure of DNA.4775

    Now, when you take these two strands that are hooked together, it ends up twisting and coiling; we call this a double helix, or we just say it's a helix structure that we have.4780

    The double helix structure is what Watson and Crick developed and came up with, and it was an extraordinary feat to elucidate this structure and figure out how DNA works.4792

    And so, what we have here is this ribbon going along that back here (that is our sugar-phosphate backbone), and it is providing...kind of sticking out from that backbone are these bases that can link to bases on the other backbone.4806

    OK, and all of this is just by hydrogen bonding.4824

    Now, what is great about hydrogen bonds is: they are not permanent bonds--these are not covalent bonds.4826

    Hydrogen bonds can break and re-form: so an integral part of DNA and what is so brilliant about it is that it can unzip and then zip back up.4830

    And that is what is needed when it is ready to do its functions.4840

    This is a nice space-filling model; so here, we are showing...these are our bases that are linked together with the yellow and the red, or the blue and the green; those are in the middle, doing their hydrogen bonding.4846

    And, on the outside here, we have our backbone.4859

    When you look at the structure in a space-filling model, where we kind of see the space taken up by the electrons here, we see that the structure has major grooves--has large gaps, and has minor groups--has small gaps.4863

    And that is interesting, because what can happen is: we can have small molecules come in and bind with the DNA at certain places; they usually bind in the major grooves, but sometimes they bind in the minor grooves.4880

    This is called molecular recognition: remember, we have all of these side chains with all of their different properties and so on; and so, you could have a molecule come in and dock with just the right complementary natures and just the right...hydrophobic here, hydrophilic here, polar here, and so on; and they can kind of plug into the DNA.4893

    That is...when you are ready to do a transcription of DNA, you have proteins that block in there and start to do the transcription process.4916

    You can have therapeutic agents that can go lock in there to be an anti-cancer agent or something like that.4926

    So really, this is when you are looking at the function of DNA--that structure is what allows it to do the things that it needs to do.4932

    In DNA molecules, these are very, very long polymers, and they can be millions of DNA base pairs long; and, in fact, there are some cool at-home experiments you can do, where you isolate DNA strands.4941

    If you go to YouTube, and you search for "isolate DNA from strawberries" or "bananas" (I think those are the two common ones), it talks about how you smash it up, and you put in some solvent.4956

    You denature everything to kind of break apart...you need to break apart the cell walls to free the DNA.4967

    And then, you can kind of go in there and pull it out and isolate it; and you can literally--they are so long, you can actually see the strands of these molecules; so it is really a very interesting experiment.4974

    What do RNA and DNA--what function do they have?--how are they used by the body?4987

    DNA, we know, is kind of like the blueprint that we have for what is going to tell the developing creature, "Are you going to be a cactus or a fish or a human?", right?4993

    It is the DNA that determines what organism is being developed.5011

    And the way that the DNA is used--those blueprints are read--is: first we have a process of transcription.5017

    So, the DNA--the two strands separate, and RNA strands are formed; RNA, our single strand, forms.5023

    They come in, and they form a complement to the single strand of DNA; we get RNA.5035

    Transcription--when you transcribe something, you write it down--like, in a courtroom, you have a courtroom recorder who is taking notes; that is called a transcript, right?5040

    It is when you have a recording of something; so we are transcribing the DNA, taking notes on what are the different nucleotides that are on there; and then, that RNA is used to synthesize proteins.5052

    So, all the proteins that do the functions in our body--the way those proteins are made is from RNA.5068

    That process is called translation; so just like you would translate something...if you are listening to something in Spanish and you want to translate it to English, you need to kind of look and say, "OK, you are saying these words; what does that mean?" and you do it in English.5076

    So, it is then using that to translate: it is saying, "OK, here is your chunk of RNA; now what protein does that code for--what do I manufacture based on this code, the words that are there?"5092

    And that is based on the genetic code; so we have done a tremendous amount in research in breaking down the code, deciphering the code.5109

    And so, this is just a table; again, you can find a table like this in any Organic text or biochemistry text; or online, you can find them.5118

    And this is showing, based on what the bases are, what the nucleotides are on your strand, what it translates to.5127

    We look at 3 nucleotides at a time; that is called a codon; and depending on what those 3 letters are--what those three nucleotides are--it translates to a different protein.5142

    If you have either UU or UUC, those both code for phenylalanine.5156

    When this is translated eventually, it is going to take a phenylalanine and attach it to the protein.5162

    And then, it goes to say, "OK, who is my next amino acid that I should add on?"5171

    And then, it looks at the next three letters; and if you have an A and a G and a U, that means you are going to build a serine.5176

    And you can see that there is some redundancy built in--that there is not just one way to code for a serine.5183

    And there are a lot of parts of DNA that are not used for coding proteins, and there is a lot of discussion on what is the purpose of those parts of the DNA.5190

    There are so many mysteries still to solve, but it's amazing and fascinating how much has already been unraveled of the genetic code, when we take the genome.5200

    The Human Genome Project looks at the entire genome of humans and deciphers it and tries to track it down.5210

    Anyway, just a brief introduction into nucleic acids and how the organic molecules go to develop both DNA and RNA strands.5218

    So finally, let's take a look at our last class of biomolecules, and that is lipids.5231

    Lipids are triglycerides; you could also call them fats or oils--so things that are greasy.5235

    Again, this is another part of our diet, fats--and a very important part of our diet, but hopefully not something that we have too much of, because our body doesn't handle that very well.5242

    Let's take a look at the structure of fats and lipids from the chemistry point of view, and then see how they come together to function in the body (or in natural systems).5253

    Here is the structure of glycerol: glycerol has 3 carbons, and it's a triol--1, 2, 3: propane triol.5263

    And, if you take an alcohol, and you react it with fatty acids, we would call that--if we have a carboxylic acid with a really, really, really, really, really long carbon chain, we describe them as fatty, because they are hydrophobic.5271

    We can either have saturated fatty acids, meaning there are no double bonds there--remember where we describe a π bond as a point of unsaturation...so if this is saturated with hydrogen (meaning it's just an alkane chain out here), we call that saturated.5285

    And if we have one or more π bonds, we call them unsaturated.5300

    And so, what is going to happen when you have an alcohol and a carboxylic acid?--you are going to replace the OH on the carbonyl.5305

    We are going to have addition-elimination and replace the OH; so we are losing 3 molecules of water here, and we are going to form 3 esters; we are going to form a triester.5314

    And so, this is described as a triglyceride; so when you are getting blood work done or something, your level of triglycerides is something they are measuring; that is measuring the level of lipids in your blood.5326

    And we have fats (or oils, as we could describe them), and you have probably heard of saturated fats, monounsaturated fats, polyunsaturated fats...so that is simply describing how many double bonds, if any, are there in the lipid structure.5338

    The difference between a saturated fat and an unsaturated fat is: if you have a saturated fat where these are all straight chains, those tend to pack very tightly together.5357

    When you have molecules that pack very tightly together, they have high melting points; so a saturated fat will have a high melting point.5367

    And so, something with a high melting point means, at room temperature, it is not going to be melted; it is going to be a solid; so these are solid fats.5379

    What fats do we have that are solids at room temperature?--things like butter or animal fats, like lard, bacon grease--things that, at room temperature, are solids, are saturated fats.5386

    When you have unsaturated fats--when you have double bonds--that causes a kink in the structure, and these molecules can no longer pack so tightly.5410

    And if they don't pack so tightly, that means it is easier to get them to separate from one another and go into the liquid stage; and so, these are going to have lower melting points, and these are the fats that we know as liquids or oils at room temperature.5419

    Things like canola...liquid oils are things like canola oil or olive oil, vegetable oils...right?...mineral oil; those are all things that must have points of unsaturation.5432

    Now, liquid oils are healthier for you; saturated fats have some problems that aren't so heart-healthy, so that is why, in practice, it is a good idea to minimize our consumption of animal fats, of saturated fats, and stick to a diet that is high in monounsaturated or polyunsaturated fats.5453

    So, the canola oil, olive oil--those are quite good to have in our diets.5477

    OK, but it's hard to work with an oil; if you are baking, if you want to make a product--let's say you want to make an Oreo® cookie, and you want to have that nice cream in there; you can't do that with olive oil or canola oil.5481

    It would just drip all over the place, right?--so you need a solid fat that is going to have the proper consistency; it also will have a longer shelf life.5493

    These can kind of turn rancid; if you have an old bottle of vegetable oil and you open it up, you can smell, sometimes, a very bitter smell.5502

    So, these are not entirely stable, and so that is why it's best to store them in the dark, and in cool temperatures, to minimize those reactions--because these π bonds can undergo reactions in air.5512

    So a lot of times, for food manufacturers, they would take these liquid oils and do partial hydrogenation.5525

    If you have ever read the ingredients of some crackers or cakes or something like that that you might buy at the store, one of the ingredients will be partially hydrogenated soybean oil, or something like that.5534

    "Partially hydrogenated"--so that means they synthetically took this oil, which has some π bonds, and partially hydrogenated it; so that means they added hydrogen gas and some catalyst.5549

    And what would that do to a π bond?--that would add H2 across the π bond and turn it into an alkane; if you get rid of some of the kinks in the structure, that makes it a solid structure.5560

    Partially hydrogenated vegetable oil...things like Crisco oil or margarine--these are products that are man-made; they are vegetable-based, but they are solids.5571

    And so, for a long time, we thought those were preferable to saturated fats, because we knew how bad saturated fats were; but then, it turns out that that chemical reaction not only hydrogenates some of the π bonds, but it also causes isomerization sometimes.5582

    OK, the naturally occurring π bonds are going to have the cis conformation: the naturally occurring π bonds in lipids are cis.5601

    And so, when you have that cis, when they are on the same side, that is when we get the bend in the chain, right?5616

    It comes to one end, and then it goes back in the other; we get the bend, and that is how we get the lower melting point.5621

    But sometimes, the catalyst can add onto the double bond, but not add the hydrogens; but the process of adding on and coming back off ends up isomerizing the π bond to make a trans double bond.5628

    OK, and so, we call those trans fats; and quite recently, we have been learning that, actually, trans fats might be even worse for you than saturated fats.5642

    So, it might be better to have bacon instead of margarine; there is a lot going on here.5652

    But actually, the FDA has stepped in--the Food and Drug Administration has stepped in, saying that the nutrition labels that are on foods...that eventually, trans fats are going to also have to be labeled on there, because we know those are something to keep an eye out for.5657

    I think there was a lawsuit that these trans fats kind of came to the public's attention; there was a lawsuit against Oreos®, saying that the stuffing in there was no good for you because of all of those trans fats.5672

    And so, I think a lot of food science research has gone into finding just the right oils to use in there, that are healthy, yet stable, and have a good shelf life.5683

    Using palm kernel oil or some naturally occurring oils that are solids is good.5694

    The take-home message is: the more you can eliminate--minimize your fats, especially coming from processed foods, the better off you are going to be.5702

    Now, what are some things that we can do with fats?5712

    One of the things we can do is: we could do a saponification reaction.5716

    And we call it a saponification because it actually is a way that you could make soap; so, in many parts of the world, in societies where they can't just go to a grocery store and buy detergents and soaps and shampoos and that kind of thing, those societies make their own soap.5720

    And of course, historically, we would have to make our own soap if we wanted a cleaning agent.5739

    The way that you make a soap is: you start with a triglyceride (so a triglyceride has, again, glycerol with these triesters), and you react it with water and base (like sodium hydroxide).5745

    And what happens is: that base--that hydroxide--it does addition-elimination; we end up cleaving these ester bonds.5761

    We eliminate a molecule of glycerol--we get back our glycerol--and these carboxylic acid groups get released as carboxylate salts.5768

    We would protonate (this is written kind of funny--I'm sorry)...so this is an O- carboxylate salt, Na+; so we get the sodium salt here.5779

    It would make the carboxylic acid; and then, of course, in a low pH, in base, that carboxylic acid would get deprotonated, and we would get the carboxylate salt instead.5789

    And carboxylate salts act as soaps: if you take a structure like this and you put it in water, it kind of suds up and acts like a good cleaning agent.5800

    We'll look at the structure of that in just a second.5808

    But what fascinates me about this reaction--and you could do this reaction; you can, again, find it on YouTube; I'm sure you could find some great videos on how to make your own soap.5811

    And what you start with is the way that soaps were made hundreds of years ago, and still made today, like I said, in many parts of the world.5820

    The way you make soap is: you take animal fat, like lard, and you mix it with some ashes from the fire (wood ash), and you add water and you cook it.5829

    And the product you get out is soap.5850

    OK, now, the question I have...or you could use Crisco, I think--we do an experiment at Cal Poly where you use Crisco shortening and cook it up with some base, and we get a soap solution.5855

    Now, the question I had when I first read about this is, "Well, who in the world ever thought, 'You know what I'm going to use to make a soap solution?--I want to wash my clothes today: I'm going to start by putting in a bunch of lard, or some bacon grease or something--put it into my cooking pot with water; I'm going to take a handful of ashes out of this fire and throw it in there and mix it up, and somehow, that is going to make a good solution for me to clean my clothes."5867

    It is just mind-boggling to me, on how we developed this process.5892

    But the theory goes: 100 years ago, when we have clothes that we make--we have clothes made out of cotton or something, they would get dirty after a while.5896

    So, the women would want to wash them, so they would go down to the creek, or maybe make some kind of tub or make a little pool of water, and they would scrub their clothes and wash their clothes in the water--just using plain water.5906

    Of course, you need to agitate it, and so maybe they would have a board that they could use--take a board and rub it, and use that to agitate it, like a washboard.5920

    OK, and what the women would notice was that, if they had this little tub of water, as they continued to wash their clothes, let's say, over the course of the week, using this tub of water, the clothes would get easier and easier to get clean later in the week.5930

    Scrubbing, scrubbing, scrubbing on Monday--but then, by Friday, you would do just a quick scrub, and your stain comes out.5948

    And so, what was happening was: the animal fats--the greases and oils that were in their clothing, they were adding to the water; and the wood they were using to scrub was adding some of this base.5954

    So, this is like our source of hydroxide; you get potash--it's actually potassium hydroxide, I think--the most common one.5976

    The animal fats are the esters that we have, the triglycerides, so that would come from grease.5984

    What they would notice was: they said, "Well, you know what, why don't I start on Monday just by adding in some bacon grease; and then, all of a sudden, I would have a great soap solution."5990

    "I get some bubbles, and it's really easy to clean my clothes."5998

    That is how, eventually, they got to this soap-making process, where they could make soap solutions; they could precipitate out the soap and make soap bars, and shave it up and make soap shampoo or flakes or something like that.6001

    And so, to me, that is just a very interesting story on how we can make soap; an luckily, nowadays, we get to just run down to the grocery store, and we have a whole aisle full of cleaning agents that have wonderful dyes and perfumes that are in there, that make them smell good, and they work great.6015

    And hopefully, they are good on the environment; that is something that, again, chemistry research continues to improve; and so on.6034

    So anyway, we call this reaction the saponification reaction.6042

    Now, the question is: how is it that we make soap?6047

    We get these carboxylate structures, and what is it that this RCO2-...why does that give us a soapy solution, and act as a soap?6049

    If you take a look at the structure of the carboxylate salt (this is the O-, Na+), we have this hydrophilic head on it (hydrophilic because it's ionic), and then we have this long carbon chain, which is hydrophobic, because it's just an alkane or maybe an alkene, and certainly doesn't like water.6063

    And, if you take this structure and you put it in water, what is going to happen is: it's going to cluster--it's going to congregate--in such a way to make a sphere that is coated on the outside with all of the ionic portions--the hydrophilic portions--and buried inside that sphere are all the hydrophobic portions--the long carbon chains.6086

    So, this is described as a micelle; and all I have shown here is a cross-section; it looks very flat, but it's just kind of--it's a sphere.6109

    In fact, if you have one of those toys--those little Koosh® balls that looks like all rubber bands--little rubber strings that are all tied together in a circle so it makes a big ball--that is kind of what a micelle looks like.6117

    Now, water is all on the outside, interacting with the hydrophilic portion.6131

    Now, does that act as a soap?--well, if you have a solution with these micelles in it, and you introduce some grease, and you agitate it (so you put it in a washing machine and it mixes, or you scrub it on a washboard, or with your hands), what is going to happen is: that grease is going to migrate; it's going to find its way into the center of the micelle, because grease...fats and oils are hydrophobic, and they are going to find their way into the hydrophobic interior of the micelle.6136

    So now, it's going to be emulsified; it's going to be trapped in that micelle; and now, when I rinse my clothes with fresh water, the soap is going to get rinsed away, and it is going to take the grease with it.6167

    Here is a really nice image of what a micelle looks like: so all on the outside here, we have the carboxylate groups.6179

    Now, if you are looking at synthetic detergents and those sorts of things, instead of using carboxylate salts, they use other ionic parts to it; and so, that might lead to better cleaning action, better for the environment, less likely to precipitate out as soap scum--all sorts of different reasons that you want to change the molecular structure to this.6186

    But, if you were making it the old-fashioned way, from saponification of an oil to make your own soap, then you are getting the carboxylate ionic part out here.6210

    And then, inside, we have all of these very, very long hydrophobic chains.6221

    And right in the middle there is where that grease is going to work its way in when we scrub, scrub, scrub our clothes.6227

    That is why...how do we clean best?--we clean best when there is water and soap and agitation, because you want that grease to find its way into the micelles.6233

    Another application that is kind of similar to the mechanism of saponification is the synthesis of biodiesel.6245

    Now, what do we usually use as fuel for heating our home or to run our automobiles--that sort of thing?--we usually use petrochemicals; so we take crude oil; we refine that into its various boiling components; and we take the ones with a certain boiling point range (it's largely a mixture of alkanes), and that is what we use as liquid gasoline.6251

    And we put that in our cars, and we go.6274

    Now, the problem with that is: there is a finite amount of crude oil, and we don't always have access to that, and all sorts of problems.6277

    So, if we can find alternate sources of carbon compounds that we can burn and use in our cars, then that would reduce our dependency on crude oil.6287

    One option is to make what is known as biodiesel; so this is diesel--this is a fuel that is made from a biological source.6297

    So, if we take a triglyceride (one of these lipids, fats, oils, something like that)--so for example, we use a lot of oil to cook French fries at our fast food restaurant--so we have all this used oil that is just garbage, that is going to be thrown out...6305

    So, what if we could somehow take that oil and use that to power our cars?6320

    OK, well, we can't just take the oil and dump it in there, because it is not flammable in that form, and it is viscous, and all sorts of other problems.6326

    But we can convert it to biodiesel using a reaction that is very similar to the saponification reaction.6334

    The reaction we do is: again, we start with a triglyceride--any triglyceride--and we react it with three equivalents of methanol and base.6340

    Now, what is going to happen here...I should say, methoxide...you just...CH3...that is just a little easier way to see it...6350

    You can imagine the methoxide adding in and then kicking out; so once again, we are going to be freeing up a molecule of glycerol.6359

    And, at the same time, we are going to be making these methyl esters, because we are replacing...here are the ester groups that we are cleaving, and we are replacing the glycerol leaving group with a methoxy group that is coming in.6368

    And so, these are described as fatty acid (there is our fatty carboxyl acid group) methyl esters, or FAME.6382

    And this is something that could be used as biodiesel; this is another interesting reaction that you can do, and these esters are not soluble with the glycerol, so actually, as this...not saponification...it's actually a transesterification, because we are going from one ester to a new ester; so as this transesterification proceeds, the fatty acid methyl esters, the FAME components, are not soluble in the glycerol, because the glycerol is very polar and the others are quite nonpolar.6389

    They actually separate out into two layers; and so you have a layer of your biodiesel and a layer that is glycerol, that could be repurchased for something else.6425

    And so, you could take that biodiesel, and you could use it in certain automobiles.6436

    Now, typically you need to have an engine that is manufactured to take diesel fuel--diesel fuel is a little different than the gasoline we use in most of our cars.6440

    But it is interesting: I have seen a tractor running on biodiesel, and it smells like McDonald's French fries, because that was the kind of oil that they used.6451

    Some of those volatile organic compounds are still around, so it sure smelled better than burning diesel or burning gasoline; that is for sure.6464

    Now, a related biomolecule is called a phosphoglyceride; so this is now something that nature makes, and so, instead of a triglyceride, where we have three long-chain fatty esters, we have two long-chain esters and then this phosphate group.6475

    So now, what we have is: we have built into one molecule--we have this ionic polar part and these long-chain nonpolar parts; so this is going to act just like the carboxylate salts that we saw, where they are going to congregate in such a way to minimize the hydrophobic or hydrophilic interactions.6494

    OK, and one use for these--one way that those compounds aggregate is what is used in cell membranes, what is a component of cell membranes; and that is called a lipid bilayer.6522

    These will congregate in such a way that all of the long carbon chains--the hydrophobic (right?--these are all hydrophobic)...they are all going to interact together, and all of the phosphate groups, the polar groups, are going to be...6538

    Polar...actually, these are ionic and hydrophilic.6560

    So, instead of forming a micelle (which still could happen), this particular structure prefers to form a sheet, a layer; and then it is going to interact with a second layer, where the two hydrophobic regions align.6567

    And what we get is known as a lipid bilayer.6583

    It is two layers of these phospho-glycosides; and what that gives us, then, is a membrane--is a big, long surface where water is happy on one side and it's happy on the other side, but it is not happy in the interior.6586

    And what that gives us--what we have with the cell membrane--is: we have a barrier.6607

    Things can't easily transport through there; we have to work to get something to go through, because it has to pass through this hydrophobic portion.6611

    A few pictures: the bilayer acting as a barrier; this is a picture that shows some nonpolar molecules.6625

    So, if you have some nonpolar--if you ingest some nonpolar molecules, they are going to find their way into the lipid bilayer, into the interior where all of the hydrophobic chains are.6632

    And this is one theory of how certain anaesthetics work--things like ether fumes; if you take those in, you can lose consciousness.6643

    And one of the ways that is theorized that that happens is: those molecules work their way into the bilayer, causing the cell membrane to expand; and then, the reaction to that is loss of consciousness.6657

    And then, this is where we start to get...as soon as you start talking about lipid bilayers, now we are really starting to get into the world of biochemistry.6673

    Now, what we care about, as an organic chemist, is this structure; now we are looking at the carbons and hydrogens and phosphoruses and so on; we have these long hydrophobic (I just saw a little typo there) carbon chains--two strands of those on the glycerol backbone.6681

    And then, one of the phosphate groups--that is our hydrophilic head, the charged part.6701

    And so, that is kind of just drawn in a cartoon as a head with two legs; and then, those will assemble to make something like this.6709

    This is the phospholipid bilayer--two layers of that.6717

    And then, that is the component of the cell membrane; and, when you actually look at the membrane of the cell, we have all sorts of things going on here--things that are embedded in it, things that prefer...like cholesterol is really hydrophobic, so that is going to be buried into the cell membrane at certain places.6725

    Some things go across and through them; different proteins can be found there; etc.6743

    And all of this is what we have when we just draw the picture of a cell with our cytoplasm and our nucleus and so on.6747

    That perimeter that we draw on the outside is the cell membrane, and that is where we have these phospholipids coming together to form the bilayer.6755

    This is starting to get biology and biochemistry-y enough for me to check out, so hopefully, this has given you a nice background into the various biomolecules that you will see down the road, that are significant in the functions of our bodies, and so on.6767

    And hopefully, you have had enough organic chemistry background where the chemistry we talked about and the functional groups we talked about are things that made sense to you.6788

    Thanks so much for joining me, and I hope to see you again really soon; have a great day.6796