1,3-sulfur shifts: Mechanism and synthetic utility

Abstract

While allylic migrations are well known, 1,3-sulfur shifts are relatively rare. These shifts occur through a variety of mechanisms depending upon the substrate type and the reaction conditions. Radical-chain, ion-pair, dipolar, and symmetry-forbidden 1,3-sigmatropic mechanisms have all been proposed. Allylic sulfur shifts have been used in the synthesis of sulfides and sulfones of higher complexity, the stereospecific synthesis of alkenes, and the construction of ketones. This comprehensive survey of 1,3-sulfur migrations pays particular attention to the reported mechanisms and synthetic application. © 2007 Springer-Verlag Berlin Heidelberg.