Providing an updated overview of SNAr substitutions, balancing both mechanistic and synthetic viewpoints, this book gives a comprehensive account of this versatile field. The first chapter deals with a mechanistic analysis of the factors governing the feasibility of SNAr substitutions, providing useful information to predict the regio- and stereoselectivity control of the 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 s-complexes. Chapter 3 describes the new concept of superelectrophilicity which has emerged from the kinetic and thermodynamic data collected in the preceding chapters , while the numerous synthetic applications are considered in depth in the chapters that follow on intermolecular, intramolecular, and nucleophilic aromatic substitutions of hydrogen. The final chapter brings together concise yet comprehensive discussions surrounding SNAr photosubstitutions, radical substitutions, and ANRORC substitutions.
Authored by an eminently 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.
Spis treści
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 SNAr H Substitutions
Cine and Tele Substitutions
Conclusion
OTHER SNAr SUBSTITUTION PATHWAYS
SN(ANRORC) Substitutions
Radical Nucleophilic Aromatic Substitutions
Nucleophilic Aromatic Photosubstitutions
O autorze
Francois Terrier obtained his Ph D from the University Pierre et Marie Curie in Paris, France, in 1968. After postdoctoral research with Prof. Bernasconi at the University of California, Santa Cruz, he was appointed Professor at the University of Rouen. In 1991, he moved to the University of Versailles, where he held a Professorship of Organic Chemistry until 2007. His research is focused on various topics dealing with reactivity and physical organic chemistry, namely nucleophilic aromatic substitutions and sigma-complexation processes, alpha-effect nucleophiles and proton transfers at carbon. He has published over 200 papers, as well as a number of book chapters and review articles.
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