It is fair to say that the single reaction that has received the greatest attention of organic chemists is nucleophilic substitution at saturated carbon atoms. The reaction is of great synthetic utility and many individual observations had accumulated before systematic efforts at characterizing the reaction by mechanistic studies began. The task of creating a coherent mechanistic interpretation was undertaken by C. K. Ingold and E. D. Hughes in England in the 1930’s. Their studies laid the basis for current understanding.1 Since those initial investigations, organic chemists have continued to study substitution reactions, and the level of detailed information about this area is greater than for any of the other broad classes of reactions we will consider. The field provides an excellent opportunity to illustrate the application of techniques which provide mechanistic information and also is one where structure of reaction intermediates and transition states has received very careful scrutiny. From these accumulated data a very satisfactory conceptual interpretation has developed. We can provide only a small selection of these details to illustrate the general concepts. The area of nucleophilic substitution will also illustrate clearly the fact that while large conceptual treatments can outline the broad features to be expected for a given system, the precise details will reveal aspects which are characteristic of specific systems. As the chapter unfolds the reader should come to appreciate both the depth and breadth of the general conceptual understanding and the characteristics of some of the individual systems.
KeywordsNucleophilic Substitution Nucleophilic Substitution Reaction Potential Energy Diagram Phenyl Cation Solvent Nucleophilicity
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Nucleophilic Substitution Mechanisms
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