Organic Reaction Mechanisms 2013

An annual survey covering the literature dated January to December 2013

A. C. Knipe

• Publisher: Wiley
• Year: 2016
• Print ISBN:
  9781118707869
• eBook ISBN:
  9781118707708
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

Organic Reaction Mechanisms 2013, the 49th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2013.

The following classes of organic reaction mechanisms are comprehensively reviewed:

• Reaction of Aldehydes and Ketones and their Derivatives
• Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives
• Oxidation and Reduction
• Carbenes and Nitrenes
• Nucleophilic Aromatic Substitution
• Electrophilic Aromatic Substitution
• Carbocations
• Nucleophilic Aliphatic Substitution
• Carbanions and Electrophilic Aliphatic Substitution
• Elimination Reactions
• Polar Addition Reactions
• Cycloaddition Reactions
• Molecular Rearrangements

An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.

Chapter 1
Reactions of Aldehydes and Ketones and Their Derivatives

B. A. Murray

Department of Science, Institute of Technology, Tallaght (ITT Dublin), Dublin, Ireland

1. Formation and Reactions of Acetals and Related Species
2. Reactions of Glucosides
3. Reactions of Ketenes
4. Formation and Reactions of Nitrogen Derivatives
   1. Imines: Synthesis, and General and Iminium Chemistry
   2. Mannich, Mannich-type and Nitro-Mannich Reactions
   3. Other ‘Name’ Reactions of Imines
   4. Synthesis of Azacyclopropanes from Imines
   5. Alkylations and Additions of Other C-Nucleophiles to Imines
   6. Arylations, Alkenylations and Allylations of Imines
   7. Miscellaneous Additions to Imines
   8. Reduction of Imines
   9. Other Reactions of Imines
   10. Oximes, Hydrazones and Related Species
5. C–C Bond Formation and Fission: Aldol and Related Reactions
   1. Reviews of Aldols and General Reviews of Asymmetric Catalysis
   2. Asymmetric Aldols Catalysed by Proline and Its Derivatives
   3. Asymmetric Aldols Catalysed by Other Organocatalysts
   4. The Mukaiyama Aldol
   5. Other Asymmetric Aldols
   6. The Henry (Nitroaldol) Reaction
   7. The Baylis–Hillman Reaction and Its Morita-variant
   8. Other Aldol and Aldol-type Reactions
   9. Allylation and Related Reactions
   10. The Horner–Wadsworth–Emmons Reaction and Related Olefinations
   11. Alkynylations
   12. Stetter Reaction, Benzoin Condensation and Pinacol Coupling
   13. Michael Additions
   14. Miscellaneous Condensations
6. Other Addition Reactions
   1. Addition of Organozincs
   2. Arylations
   3. Addition of Other Organometallics
   4. The Wittig Reaction
   5. Hydrocyanation, Cyanosilylation and Related Additions
   6. α-Aminations and Related Reactions
   7. Miscellaneous Additions
7. Enolization, Reactions of Enolates and Related Reactions
   1. α-Halogenation, α-Alkylation and Other α-Substitutions
8. Oxidation and Reduction of Carbonyl Compounds
   1. Oxidation of Aldehydes to Acids
   2. Oxidation of Aldehydes to Amides, Esters and Related Functional Groups
   3. Baeyer–Villiger and Other Oxidation Reactions of Ketones
   4. Miscellaneous Oxidative Processes
   5. Reduction Reactions
   6. Stereoselective Reduction Reactions
9. Other Reactions
10. References

Formation and Reactions of Acetals and Related Species

Equilibria for the formation of hemiacetals from eight isomeric hexanals have been measured in methanol, and compared with the steric environment around the aldehyde.¹ Kinetic studies have also been carried out, and these suggest an early TS.

Catalytic asymmetric acetalization of aldehydes has been demonstrated, using large chiral BINOL-derived phosphoric acid catalysts: these are proposed to generate confined chiral microenvironments.²

A new enantioselective arylation of enecarbamates (1) has been developed, using a quinone imine acetal (2) as a functionalized surrogate aromatic, and an axially chiral BINAP-dicarboxylic acid catalyst.³ The useful α-amino-β-aryl ether products (3) are formed in up to 99% ee, and des often >90%, and are further transformable into chiral β-aryl amines and α-aryl esters. Mechanistically revealing observations include: (i) trans-enecarbamate switches the sense of asymmetric induction; (ii) the NH in (1) is critical, presumably for hydrogen bonding to catalyst: the NMe starter fails; and (iii) crossover experiments fail, implicating an intramolecular route. The proposed first step is a highly stereoselective C–C bond formation followed by aromatization (with elimination of R³-OH), the...

Table of contents

• Cover
• Title Page
• Copyright
• Table of Contents
• Contributors
• Preface
• Chapter 1: Reactions of Aldehydes and Ketones and Their Derivatives
• Chapter 2: Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives
• Chapter 3: Oxidation and Reduction
• Chapter 4: Carbenes and Nitrenes
• Chapter 5: Aromatic Substitution
• Chapter 6: Carbocations
• Chapter 7: Nucleophilic Aliphatic Substitution
• Chapter 8: Carbanions and Electrophilic Aliphatic Substitution
• Chapter 9: Elimination Reactions
• Chapter 10: Addition Reactions: Polar Addition
• Chapter 11: Addition Reactions: Cycloaddition
• Chapter 12: Molecular Rearrangements
• Author Index
• Subject Index
• End User License Agreement