Stereocontrolled Aldol-Like Reactions Involving Oxocarbenium Intermediates

Abstract

AbstractOxocarbenium cations are key intermediates for the stereocontrolled construction of carbon–carbon bonds. In particular, we have developed a wide range of stereoselective aldol-like processes that take advantage of the high reactivity of the oxocarbenium species arising from acetals, glycals, and orthoesters with metal enolates. This Account describes the development and optimization of such processes, together with other significant contributions, with a particular emphasis on their application to the synthesis of natural products.1 Introduction2 Substrate-Controlled Processes2.1 Additions to Acyclic Acetals2.2 Additions to Cyclic Acetals3 Chiral-Auxiliary-Based Processes3.1 Additions to Acyclic Acetals3.2 Additions to Cyclic Acetals and Glycals4 Chiral-Catalysis-Based Processes4.1 Organocatalysis4.2 Metal Catalysis5 Conclusions