Copper-catalyzed selective radical-radical cross-coupling for C-S bond formation: an access to alpha-alkylthionitriles

A new protocol for C-S bond formation was developed by selective cross-coupling between a thiyl radical and an isobutyronitrile radical. Using this strategy, a series of valuable a-alkylthionitrile derivatives were synthesized from basic starting materials. Preliminary mechanistic investigation was performed by EPR and XAFS, revealing that the transient thiyl radical could be stabilized by a copper catalyst to a persistent one. Therefore, on the basis of the persistent radical effect, selective radical-radical cross-coupling between the thiyl radical and the isobutyronitrile radical was achieved successfully in this work.