Iridium-Catalyzed Oxidative Heteroarylation of Arenes and Alkenes: Overcoming the Restriction to Specific Substrates

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A great challenge in transition metal-catalyzed oxidative Ar–H/Ar–H cross-coupling chemistry is to develop privileged catalytic platforms for overcoming the restriction to specific substrates. Reported herein is a Cp*Ir(III) catalytic platform for the broad C–H ortho-heteroarylation of arenes with up to 16 types of directing groups. The power of the platform is further demonstrated by the (Z)-selective heteroarylation of enamides, which is clearly different from the methods where the catalytic chain begins with the metalation of heteroarene leading to (E)-selective product. Unlike the Rh(III)/Rh(I) catalytic version, the stoichiometric reactions of cyclometalated iridium(III) species with benzothiophene suggest an oxidatively induced reductive elimination involving a high-valent diaryl–iridium intermediate. The catalytic platform overcomes the restriction to specific substrates and would be synthetic chemists’ toolbox for the construction of aryl–heteroaryl and vinyl–heteroaryl linkages.