From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement

Ignacio Colomer, Marina Velado, Roberto Fernández de la Pradilla, Alma Viso

Index: 10.1021/acs.chemrev.7b00428

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Abstract

The [2,3]-sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally shifted toward the sulfoxide. In the presence of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions. In most cases, a good transfer of stereochemical information through an ordered transition state is obtained. Furthermore, the ease of coupling this process with other versatile, stereocontrolled reactions has enhanced the usefulness of this protocol. This review aims to provide a comprehensive survey of this rearrangement and its application in the synthesis of natural and bioactive products.