We have developed the N-heterocyclic carbene/organic photoredox-cocatalyzed acyl azolation of styrenes using acyl azoles. The cooperative action of organic photoredox catalysis and NHC catalysis enabled the C–N bond cleavage of the acyl azole and the insertion of the C–C double bond in styrene with complete regioselectivity. Radical cation species, generated by single electron oxidation of alkene, subsequently reacted with nitrogen nucleophile and ketyl radical intermediate to accomplish insertion of alkene into C–N bond.
DOI: 10.1021/acs.orglett.5c01533