S-Alkylation of sulfinamides with Zn-carbenoids: expanding stereoselective sulfoximine synthesis beyond NH derivatives†

Abstract

Sulfoximines are experiencing steadily increasing use in the development of pharmaceuticals and agrochemicals. Although recently a number of synthetic methods to access this versatile motif have been disclosed, only NH-sulfoximines have been considered as the ultimate targets. Here, we report an approach toward enantiopure N-substituted sulfoximines via direct stereoretentive S-alkylation of parent sulfinamides with zinc carbenoids. Mechanistically, a carbon–sulfur bond is formed in the course of 1,2-metallate rearrangement featuring an unusual migration of the S-atom in the transient zincate complex. The approach accommodates a large variety of differently substituted sulfinamides and features excellent functional group compatibility.