Synthesis of α,α-Disulfenylated Aldehydes via Oxidative Transformation of Tertiary Amines

A method for the copper-catalyzed regioselective β-functionalization of tertiary amines with thiophenols has been developed. The control experiments and primary studies show that a thiyl radical is involved in the reaction, and the method provides a novel and direct approach to synthesize C­(sp3)–S bonds without a directing group under ligand-free conditions.