S-Benzylation of Sulfenamides with Tertiary Amine Using Methyl Propiolate as a Bifunctional Additive

Sulfilimines serve as key intermediates in the synthesis of pharmacologically and agriculturally relevant motifs. We herein report a practical and efficient protocol for the synthesis of sulfilimines via deaminative sulfur benzylation without the addition of a metal catalyst and a base. In the reaction, employing methyl propionate as a bifunctional reagent to activate the amino and sulfenamide groups enables the chemoselective coupling of various sulfenamides with tertiary amines, delivering the target products in high yield with excellent selectivity.