Photochemical halogen-bonding assisted generation of vinyl and sulfur-centered radicals: stereoselective catalyst-free C(sp2)-S bond forming reactions

Abstract

The combination of photochemistry and halogen bonding interactions has risen in the last few years as a powerful synthetic tool for the creation of radical intermediates under mild conditions. In the formation of carbon-centered radicals, this reactivity has been to date restricted to the employment of aryl and alkyl halides as precursors. We now envisioned that the halogen-bonding initiated formation of highly reactive vinyl radicals would be a feasible process for the photochemical cross-coupling between thiols and alkenyl halides under basic conditions. The reaction shows indeed a very broad functional group tolerance, is stereoselective, simple and scalable. In-depth mechanistic studies point at the formation of vinyl and sulfur-centered radicals as the intermediates of the reaction and DFT calculations support the pre-formation of a halogen-bonding complex as the initiator of the photochemical transformation. Synthetic applications were developed to extend the utility of this methodology.