Abstract

Asymmetric organocatalysis, in which small chiral organic molecules are used as catalysts for the stereocontrolled assembly of structurally diverse molecules, has emerged as a powerful tool in contemporary organic synthesis. Asymmetric organocatalysis is remarkable both for the variety of its modes of activation and for the structural simplicity of most organocatalysts, a feature that has been crucial for the generation of mechanistic working models. From a mechanistic perspective, organocatalytic modes of activation can be classified according to (a) the covalent or noncovalent character of the substrate—catalyst interaction, and (b) the chemical nature of the organocatalyst. This chapter presents an overview of the most important, currently accepted mechanistic features of the modes of activation operative in asymmetric organocatalysis.

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