Advanced Organic Chemistry Pt. B : Reactions and Synthesis

by Carey

• ISBN13: 9780306434570
• ISBN10: 0306434571
• Edition: 3rd
• Format: Paperback
• Copyright: 1990-09-01
• Publisher: Kluwer Academic Pub

Table of Contents

List of Figures

List of Tables

List of Schemes

Chapter 1. Alkylation of Nucleophilic Carbon. Enolates and Enamines

1.1. Generation of Carbanions by Deprotonation

1.2. Regioselectivity and Stereoselectivity in Enolate Formation

1.3. Other Means of Generating Enolates

1.4. Alkylation of Enolates

1.5. Generation and Alkylation of Dianions

1.6. Medium Effects in the Alkylation of Enolates

1.7. Oxygen versus Carbon as the Site of Alkylation

1.8. Alkylation of Aldehydes, Esters, Amides, and Nitriles

1.9. The Nitrogen Analogs of Enols and Enolates--Enamines and Imine Anions

1.10. Alkylation of Carbon Nucleophiles by Conjugate Addition

General References

Problems

Chapter 2. Reactions of Carbon Nucleophiles with Carbonyl Groups

2.1. Aldol Condensation

2.1.1. The General Mechanism

2.1.2. Mixed Aldol Condensations with Aromatic Aldehydes

2.1.3. Control of Regiochemistry and Stereochemistry of Mixed Aldol Condensations of Aliphatic Aldehydes and Ketones

2.1.4. Intramolecular Aldol Condensations and the Robinson Annulation

2.2. Condensation Reactions of Imines and Iminium Ions

2.2.1. The Mannich Reaction

2.2.2. Amine-Catalyzed Condensation Reactions

2.3. Acylation of Carbanions

2.4. The Witting and Related Reactions

2.5. Reactions of Carbonyl Compounds with a-Trimethylsilyl Carbanions

2.6. Sulfur Ylides and Related Nucleophiles

2.7. Nucleophilic Addition-Cyclization

General References

Problems

Chapter 3. Functional Group Interconversion by Nucleophilic Substitution

3.1. Conversion of Alcohols to Alkylating Agents

3.1.1. Sulfonate Esters

3.1.2. Halides

3.2. Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon

3.2.1. General Solvent Effects

3.2.2. Nitriles

3.2.3. Azides

3.2.4. Alkylation of Amines and Amides

3.2.5. Oxygen Nucleophiles

3.2.6. Sulfur Nucleophiles

3.2.7. Phosphorus Nucleophiles

3.2.8. Summary of Nucleophilic Substitution at Saturated Carbon

3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters

3.4. Interconversion of Carboxylic Acid Derivatives

3.4.1. Preparation of Reaction Reagents for Acylation

3.4.2. Preparation of Esters

3.4.3. Preparation of Amides

Problems

Chapter 4. Electrophilic Additions to Carbon-Carbon Multiple Bonds

4.1. Addition of Hydrogen Halides

4.2. Hydration and Other Acid-Catalyzed Additions

4.3. Oxymercuration

4.4. Addition of Halogens to Alkenes

4.5. Electrophilic Sulfur and Selenium Reagents

4.6. Addition of Other Electrophilic Reagents

4.7. Electrophilic Substitution Alpha to Carbonyl Groups

4.8. Additions to Allenes and Alkynes

4.9. Addition at Double Bonds via Organoboranes

4.9.1. Hydroboration

4.9.2. Reactions of Organoboranes

4.9.3. Enantioselective Hydroboration

4.9.4. Hydroboration of Alkynes

General References

Problems

Chapter 5. Reduction of Carbonyl and Other Functional Groups

5.1. Addition of Hydrogen

5.1.1. Catalytic Hydrogenation

5.1.2. Other Hydrogen-Transfer Reagents

5.2. Group III Hydride-Donor Reagents

5.2.1. Reduction of Carbonyl Compounds

5.2.2. Reduction of Other Functional Groups by Hydride Donors

5.3. Group IV Hydride Donors

5.4. Hydrogen Atom Donors

5.5. Dissolving-Metal Reductions

5.5.1. Addition of Hydrogen

5.5.2. Reductive Removal of Functional Groups

5.5.3. Reductive Carbon-Carbon Bond Formation

5.6. Reductive Deoxygenation of Carbonyl Groups

General References

Problems

Chapter 6. Cycloaddition, Unimolecular Rearrangements, and Thermal Eliminations

6.1. Cycloaddition Reactions

6.1.1. The Diels-Alder Reaction: General Features

6.1.2. The Diels-Alder Reaction: Dienophiles

6.1.3. The Diels-Alder Reaction: Dienes

6.1.4. Intramolecular Diels-Alder Reactions

6.2. Dipolar Cycloaddition Reactions

6.3. [2 + 2] Cycloadditions and Other Reactions Leading to Cyclobutanes

6.4. Photochemical Cycloaddition Reactions

6.5. [3,3]-Sigmatropic Rearrangements: Cope and Claisen Rearrangements

6.6. [2,3]-Sigmatropic Rearrangements

6.7. Ene Reactions

6.8. Unimolecular Thermal Elimination Reactions

6.8.1. Cheletropic Elimination

6.8.2. Decomposition of Cyclic Azo Compounds

6.8.3. ß-Eliminations Involving Cyclic Transition States

General References

Problems

Chapter 7. Organometallic Compounds of Group I and II Metals

7.1. Preparation and Properties of Organolithium and Organomagnesium Compounds

7.2. Reactions of Organolithium and Organomagnesium Compounds

7.2.1. Reactions with Alkylating Agents

7.2.2. Reactions with Carbonyl Compounds

7.3. Organic Derivatives of Group IIB Metals

7.3.1. Organozinc Compounds

7.3.2. Organocadmium Compounds

7.3.3. Organomercury Compounds

7.4. Organocerium Compounds

General References

Problems

Chapter 8. Reactions Involving the Transition Metals

8.1. Reactions Involving Organocopper Intermediates

8.2. Reactions Involving Organopalladium Intermediates

8.3. Reactions Involving Organonickel Compounds

8.4. Reactions Involving Rhodium, Iron, and Cobalt

8.5. Organometallic Compounds with p Bonding

General References

Problems

Chapter 9. Carbon-Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin

9.1. Organoboron Compounds

9.1.1. Synthesis of Organoboranes

9.1.2. Carbon-Carbon Bond-Forming Reactions

9.2. Organosilicon Compounds

9.2.1. Synthesis of Organosilanes

9.2.2. Carbon-Carbon Bond-Forming Reactions

9.3. Organotin Compounds

9.3.1. Synthesis of Organostannanes

9.3.2. Carbon-Carbon Bond-Forming Reactions

General References

Problems

Chapter 10. Reactions Involving Highly Reactive Electron-Deficient Intermediates

10.1. Reactions Involving Carbocation Intermediates

10.1.1. Carbon-Carbon Bond-Formation Involving Carbocations

10.1.2. Rearrangements of Carbocations

10.1.3. Related Rearrangements

10.1.4. Fragmentation Reactions

10.2. Reactions Involving Carbenes and Nitrenes

10.2.1. Structure and Reactivity of Carbenes

10.2.2. Generation of Carbenes

10.2.3. Addition Reactions

10.2.4. Insertion Reactions

10.2.5. Rearrangement Reactions

10.2.6. Related Reactions

10.2.7. Nitrenes and Related Intermediates

10.2.8. Rearrangements to Electron-Deficient Nitrogen

10.3. Reactions Involving Free-Radical Intermediates

10.3.1. Sources of Radical Intermediates

10.3.2. Introduction of Functionality by Radical Reactions

10.3.3. Addition Reactions of Radicals with Substituted Alkenes

10.3.4. Cyclization of Free-Radical Intermediates

10.3.5. Fragmentation and Rearrangement Reactions

General References

Problems

Chapter 11. Aromatic Substitution Reactions

11.1. Electrophilic Aromatic Substitution

11.1.1. Nitration

11.1.2. Halogenation

11.1.3. Friedel-Crafts Alkylations and Acylations

11.1.4. Electrophilic Metalation

11.2. Nucleophilic Aromatic Substitution

11.2.1. Aromatic Diazonium Ions as Synthetic Intermediates

11.2.2. Substitution by the Addition-Elimination Mechanism

11.2.3. Substitution by the Elimination-Addition Mechanism

11.2.4. Copper-Catalyzed Reactions

11.3. Aromatic Radical Substitution Reactions

11.4. Substitution by the SRN1 Mechanism

Problems

Chapter 12. Oxidations

12.1. Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids

12.1.1. Transition Metal Oxidants

12.1.2. Other Oxidants

12.2. Addition of Oxygen at Carbon-Carbon Double Bonds

12.2.1. Transition Metal Oxidants

12.2.2. Epoxides from Alkenes and Peroxidic Reagents

12.2.3. Subsequent Transformations of Epoxides

12.2.4. Reactions of Alkenes with Singlet Oxygen

12.3. Cleavage of Carbon-Carbon Double Bonds

12.3.1. Transition Metal Oxidants

12.3.2. Ozonolysis

12.4. Selective Oxidative Cleavages at Other Functional Groups

12.4.1. Cleavage of Glycols

12.4.2. Oxidative Decarboxylation

12.5. Oxidation of Ketones and Aldehydes

12.5.1. Transition Metal Oxidants

12.5.2. Oxidation of Ketones and Aldehydes by Oxygen and Peroxidic Compounds

12.5.3. Oxidation with Other Reagents

12.6. Allylic Oxidation

12.6.1. Transition Metal Oxidants

12.6.2. Other Oxidants

12.7. Oxidations at Unfunctionalized Carbon

General References

Problems

Chapter 13. Multistep Syntheses

13.1. Protective Groups

13.1.1. Hydroxyl-Protecting Groups

13.1.2. Amino-Protecting Groups

13.1.3. Carbonyl-Protecting Groups

13.1.4. Carboxy Acid-Protecting Groups

13.2. Synthetic Equivalent Groups

13.3. Synthetic Analysis and Planning

13.4. Control of Stereochemistry

13.5. Illustrative Syntheses

13.5.1. Juvabione

13.5.2. Longifolene

13.5.3. Prelog-Djerassi Lactone

13.5.4. Aphidicolin

General References

Problems

References for Problems

Index