Tandem Transformations Initiated by the Migration of a Silyl Group. Some New Synthetic Applications of Silyloxiranes

Abstract

The trimethylsilyl group and other silicon-containing groups are able to migrate to anionic centers within the molecule. This phenomenon is used to generate tandem processes involving a silyl group migration - a leaving group elimination in systems equipped with a silyl-, oxido-, and leaving group. Applications of silyloxiranes to synthesis involving tandem processes are described. Other synthetic applications of silyloxiranes based upon the cooperative reactions of silyl-, oxido (hydroxy) and leaving group are discussed. 1. Introduction 2. Reaction of (trimethylsilyl)oxiranes with α-sulfonyl- and related anions 3. Synthesis of polyols, involving tandem silyl group migration - elimination reactions 4. Oxidation of (trimethylsilyl)oxiranes into α-hydroxyaldehyde or acylsilane derivatives 5. Reaction of (triphenylsilyl)oxirane with α-sulfonyl anions and synthetic applications of the adducts 6. Conclusions