Copper-Catalyzed Transfer Markovnikov Hydrothiolation of Alkenes.

A copper(II) triflate catalyzed transfer hydromethylthiolation of alkenes has been developed using commercially available and easy-to-handle β-methylthioketone as the methanethiol donor under air. This method exclusively provides Markovnikov products. The reaction demonstrates a broad substrate scope and excellent functional group tolerance, including compatibility with natural product derivatives. Furthermore, methylthioethers synthesized by this protocol were successfully applied to the preparation of diverse sulfur-containing compounds as well as bioactive molecules.