Modern Nucleophilic Aromatic Substitution

  • ID: 2379402
  • Book
  • 488 Pages
  • John Wiley and Sons Ltd
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This book provides a comprehensive overview of nucleophilic aromatic substitutions, focusing on the mechanistic and synthetic features that govern these reactions. The first chapter presents a detailed mechanistic analysis of the factors determining the feasibility of SNAr substitutions, providing decisive information to predict regioselectivity of many reactions and to define the conditions for concerted SNAr processes. Reflecting the key role played by these species as intermediates in most SNAr reactions, chapter 2 then discusses the chemistry of anionic sigma–complexes. Chapter 3 describes the concept of superelectrophilicity in SNAr substitutions, as it has recently emerged from the reactivity of strongly electron–deficient aromatic and heteroaromatic structures. The numerous synthetic applications are considered in depth in the chapters 4 and 5 that follow on intermolecular and intramolecular nucleophilic aromatic substitutions. Then, chapter 6 focuses on substitutions proceeding formally through displacement of a hydride ion, a hot topic in the field. The final chapter brings together concise yet comprehensive discussions surrounding SNAr photosubstitutions, radical substitutions, and ANRORC substitutions.

Authored by a highly respected chemist who has contributed greatly to the field over the past two decades, this is a valuable information source for all organic chemists working in academia or the pharmaceutical and agrochemical industries.

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THE SNAr REACTIONS: MECHANISTIC ASPECTS

Introduction

Activation of the Aromatic System: Driving Force for SNAr Reactions

Leaving Group, Nucleophile, Solvent, and Medium Effects

Effects of Specific Structural Variations in the Activated Ring

Spectral Evidence for the Intermediacy of sigma–Complexes in SNAr Reactions

Base Catalysis in SNAr Reactions

Regioselectivity in SNAr Reactions

Asymmetric SNAr Substitutions

Concerted SNAr Substitutions

Conclusion

STRUCTURE AND REACTIVITY OF ANIONIC SIGMA–COMPLEXES

Introduction

Structural Features of sigma–Complexes

Thermodynamics and Kinetics of sigma–Complex Formation

THE SUPERELECTROPHILIC DIMENSION IN SNAr AND RELATED SIGMA–COMPLEXATION PROCESSES

Introduction

The Classical Domain of SNAr and Anionic sigma–Complexation Reactivity

Reaching the Superelectrophilic Dimension

The Synthetic Potential of sigma–Complexation and SNAr Reactivity in the Superelectrophilic Dimension

Origin of the Superelectrophilicity of Neutral 10pi Heteroaromatics

SYNTHETIC ASPECTS OF INTERMOLECULAR SNAr REACTIONS

Introduction

Intermolecular Displacements of a Nitro Group

Intermolecular Displacements of Halogen and Other Leaving Groups

Conclusion

INTRAMOLECULAR SNAr REACTIONS

Introduction

SNAr Cyclizations

Smiles Rearrangements

Conclusion

NUCLEOPHILIC AROMATIC SUBSTITUTIONS OF HYDROGEN

Introduction

Reactions Involving Oxidation of sigma–Complex–Type Intermediates

Vicarious Nucleophilic Aromatic Substitutions of Hydrogen (VNS)

Deoxygenative SNArH Substitutions

Cine and Tele Substitutions

Conclusion

OTHER SNAr SUBSTITUTION PATHWAYS

SN(ANRORC) Substitutions

Radical Nucleophilic Aromatic Substitutions

Nucleophilic Aromatic Photosubstitutions

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Francois Terrier
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