Utilizing Carbonyl Coordination of Native Amides for Palladium-Catalyzed C(sp(3))-H Olefination

摘要

Pd-II-catalyzed C(sp(3))-H olefination of weakly coordinating native amides is reported. Three major drawbacks of previous C(sp(3))-H olefination protocols, 1) in situ cyclization of products, 2) incompatibility with alpha-H-containing substrates, and 3) installation of exogenous directing groups, are addressed by harnessing the carbonyl coordination ability of amides to direct C(sp(3))-H activation. The method enables direct C(sp(3))-H functionalization of a wide range of native amide substrates, including secondary, tertiary, and cyclic amides, for the first time. The utility of this process is demonstrated by diverse transformations of the olefination products.