Rhodium-Catalyzed 1,1-Arylesterification of Unactivated Alkenes with Dinucleophiles

Recent advances have significantly expanded the scope of alkene functionalization reactions. In contrast to the well-established 1,2-difunctionalization, the 1,1-difunctionalization of alkenes presents greater synthetic challenges. Herein, we disclose a rhodium-catalyzed 1,1-arylesterification of alkenes with two different nucleophiles. By the catalysis of rhodium(III), diaryl tertiary alcohol undergoes β-C elimination, followed by sequential olefin migration insertion, elimination, and reinsertion processes. Subsequent coordination of a second nucleophile to the rhodium center ultimately yielded 1,1-difunctionalized products through a cascade elimination. The addition of rhodium(III) and AgOAc in this procedure is crucial for achieving selective C-C bond cleavage and reconstruction, addressing the challenge of the two nucleophiles in difunctionalization. Moreover, this reaction exhibits broad substrate scope and high functional group tolerance. The mechanistic investigations confirm that this procedure involves C(<i>sp</i>³)-C(<i>sp</i>²) bond selective breaking, β-H elimination, and hydride reinsertion pathways.