Metal-Free Oxidative Thioesterification of Methyl Ketones with Thiols/Disulfides for the Synthesis of α-Ketothioesters.

A direct Csp3-H bond oxidative thioesterification of methyl ketones with aromatic thiols/disulfides promoted by TBAI/K2S2O8 has been developed. The reaction provides successfully a simple and efficient method for the synthesis of functionalized α-ketothioesters of aromatic thiols. This practical methodology exhibits readily available starting materials, large-scale applicability, synthetic application, and broad functional group tolerance. A possible mechanism for the transformation is proposed.