Modern nucleophilic aromatic substitution / François Terrier.

Format:

Book

Author/Creator:

Terrier, François.

Language:

English

Subjects (All):

Substitution reactions.

Aromatic compounds.

Physical Description:

1 online resource (488 p.)

Edition:

1st ed.

Place of Publication:

Weinheim, Germany : Wiley-VCH, 2013.

Language Note:

English

Summary:

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. Chap

Contents:

Modern Nucleophilic Aromatic Substitution; Contents; Preface; 1 The SNAr Reactions: Mechanistic Aspects; 1.1 Introduction; 1.2 Activation of the Aromatic System: Driving Force for SNAr Reactions; 1.2.1 Benzene and Related Arene Derivatives; 1.2.2 Pyridine and Related Aza-aromatics; 1.2.3 Five-Membered Ring Heterocycles; 1.2.4 Activation by Electron-Withdrawing Heterocyclic Units: The Superelectrophilic Dimension in SNAr Substitutions; 1.3 Leaving Group, Nucleophile, Solvent, and Medium Effects; 1.3.1 The Influence of the Leaving Group; 1.3.1.1 Halogen Nucleofugality

1.3.1.2 The Mobility of the Nitro Group and Other Leaving Groups1.3.2 The Influence of the Nucleophile; 1.3.2.1 Basicity and Polarizability; 1.3.2.2 Ritchie and Mayr's Scales; 1.3.3 The Influence of the Solvent; 1.3.3.1 SNAr Reactions Involving Anionic Nucleophiles; 1.3.3.2 SNAr Reactions Involving Neutral Nucleophiles; 1.4 Effects of Specific Structural Variations in the Activated Ring; 1.4.1 ortho versus para Activation: Hydrogen Bonding and Built-in Solvation; 1.4.2 Reactivity at Unsubstituted versus Substituted Ring Carbon Atoms: Side Processes

1.5 Spectral Evidence for the Intermediacy of o-Complexes in SNAr Reactions1.6 Base Catalysis in SNAr Reactions; 1.6.1 The Specific Base-General Acid Mechanism; 1.6.2 The Rate-Limiting Proton-Transfer Mechanism; 1.7 Regioselectivity in SNAr Reactions; 1.8 Asymmetric SNAr Substitutions; 1.9 Concerted SNAr Substitutions; 1.9.1 Ring Activation and Feasibility of Concerted Substitutions; 1.9.2 Concerted Substitutions in Triazines; 1.10 Conclusion; References; 2 Structure and Reactivity of Anionic o-Complexes; 2.1 Introduction; 2.2 Structural Features of o-Complexes; 2.2.1 X-Ray Crystallography

2.2.2 Gas-Phase Meisenheimer Complexes2.2.3 NMR Spectroscopy; 2.2.3.1 Complexation at Unsubstituted Carbons; 2.2.3.2 Complexation at Substituted Carbons; 2.2.3.3 Complexation versus Proton Abstraction; 2.3 Thermodynamics and Kinetics of o-Complex Formation; 2.3.1 The Nature of the Aromatic System; 2.3.2 The Effect of Ring Substituents; 2.3.3 Nucleophilic Reactivity at Substituted versus Unsubstituted Carbons: Steric Effects; 2.3.3.1 Relative Reactivities and Stabilities of 1-Substituted and 1,1-Disubstituted Complexes

2.3.3.2 Isomeric Addition at Substituted and Unsubstituted Carbons of Electron-Deficient Aromatics: Relevance to Nucleophilic Aromatic Substitution Processes2.3.4 Intramolecular Additions: Spiro Complexes; 2.3.5 Diadduct Formation: Meta Bridging; 2.3.6 The Effect of the Nucleophile; 2.3.7 Solvent and Medium Effects; References; 3 The Superelectrophilic Dimension in SNAr and Related o-Complexation Processes; 3.1 Introduction; 3.2 The Classical Domain of SNAr and Anionic o-Complexation Reactivity; 3.3 Reaching the Superelectrophilic Dimension; 3.3.1 The Reference Water Reaction

3.3.2 o-Complexation with Weak Carbon Nucleophiles

Notes:

Description based upon print version of record.

Includes bibliographical references and index.

ISBN:

9783527656141

3527656146

9783527656165

3527656162

9783527656172

3527656170

OCLC:

850163696