Photoinduced Mn catalysis for efficient platform for C-heteroatom bond coupling of aryl halides

Abstract Photoinduced transition metal catalysis offers innovative strategies for fostering novel chemical reactions and improving established ones. In this work, we present a highly efficient, photoinduced Mn(II)-bipyridine catalyzed C–N, C-O and C-S coupling reaction between aryl halides—particularly less reactive aryl chlorides—and nucleophiles containing nitrogen, oxygen, and sulfur. This protocol does not need an external photocatalyst, as the single Mn(II)–bipyridine complex simultaneously serves as both the light-harvester and the metal catalyst. This method exhibits excellent substrate scope, covering eight different nitrogen sources for C-N coupling, as well as C-O coupling with alcohols, C-S coupling with thiophenols, encompassing more than 150 examples, with yields reaching up to 94%. Mechanistic studies suggest that this reaction may be initiated and sustained by the Mn(I) species through the photoinduced homolysis of the catalyst precursor bipyridine-Mn(II)(OAc) 2 , likely proceeding via a Mn(I)/Mn(III) catalytic cycle.