Rhodium(III)-Catalyzed Cascade Redox-Neutral C-H Functionalization and Aromatization: Synthesis of Unsymmetrical ortho-Biphenols

An efficient rhodium(III)-catalyzed coupling reaction of N-aryloxyacetamides with 6-diazo-2-cyclohexenones through a cascade redox-neutral C-H functionalization and aromatization has been developed. This novel and scalable transformation provides a straightforward way to construct unsymmetrical ortho-biphenols with broad substrate scope under mild and redox-neutral conditions. The synthetic utility of this approach is demonstrated in the late-stage functionalization of bioactive compounds and the synthesis of an optically active ortho-biphenol.