Recent Developments in Stereoselective Reactions of Sulfonium Ylides

Abstract

This review describes advances in the literature since the mid-1990s in the area of reactions of sulfonium ylide chemistry, with particular attention paid to stereoselective examples. Although the chemistry of sulfonium ylides was first popularized and applied in a substantial way in the 1960s, there has been sustained interest in the chemistry of sulfonium ylides since then. Many new ways of exploiting sulfonium ylides in productive stereoselective methodologies have emerged, often taking advantage of advances in organocatalysis and transition metal catalysis, to access stereodefined structurally complex motifs. The development of many different chiral sulfides over the last 20–30 years has also played a role in accelerating their study in a variety of reaction settings. In general, formal cycloaddition reactions ([2 + 1] and [4 + 1]) of sulfonium ylides follow a similar mechanistic pathway: initial addition of the nucleophilic ylide carbanion to an electrophile to form a zwitterionic betaine intermediate, followed by cyclization of the zwitterionic intermediate to afford the desired three-membered cyclic product (e.g., epoxide, cyclopropane, or aziridine), five-membered monocyclic (e.g., oxazolidinone), or fused bicyclic product (e.g., benzofuran, indoline).

Keywords

• sulfonium
• ylides
• conjugate addition
• epoxide
• cyclopropane
• aziridine