Electrochemical dehydrogenative phosphorothiolation of heteroarenes

An electrochemical dehydrogenative phosphorothiolation of heteroarenes for the synthesis of S-heteroaryl phosphorothioates has been developed. The reaction employs elemental sulfur as the S-source. By avoiding the use of transition-metal catalysts, base, external oxidants, highly toxicity and sensitivity of the reagents, a variety of S-heteroaryl phosphorothioates have been prepared. This phosphorothiolation reaction shows high functional group compatibility, and can be easily scaled-up to gram quantities. [Display omitted] •A convergent strategy integrating C(sp2)-H and C(sp3)-H phosphorothiolation.•Simple and readily available elemental sulfur as the S-source.•Avoids the use of transition-metal catalysts, chemical redox agents and hazardous reaction media.•High functional group compatibility.