Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substra...Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity to the alkene moieties, due to the preference for formation of kinetically stable five-membered metallacycles. Herein, we have disclosed a complementary strategy to accomplish a nickel-catalyzed remote arylalkylation of alkenyl amines with excellent regioselectivity and diastereofidelity, involving rare six- or seven-membered metallacycles. This general protocol is compatible with a series of δ- and ε-alkenyl amines, providing corresponding valuable δ,ε- and ε,ζ-difunctionalized aliphatic amines that would be difficult to synthesize. The coordination of the bidentate picolinamide auxiliary and the facile oxidative addition of alkyl halides to Ni(I) species are the key to the success of the developed remote olefin dicarbofunctionalization.展开更多
基金This work was supported by the National Natural Science Foundation of China(21901185,22002037)the Innovation and Entrepreneurship Training Programme for University Students(202110546007)+1 种基金the Scientific Research Hunan Provincial Education Department(19A068)funds provided by Tianjin Normal University.
文摘Directing group-assisted, transition metal-catalyzed three-component difunctionalization of alkenes has emerged as a powerful tool to drive molecular complexity. However, this strategy generally works with the substrates bearing directing groups in close proximity to the alkene moieties, due to the preference for formation of kinetically stable five-membered metallacycles. Herein, we have disclosed a complementary strategy to accomplish a nickel-catalyzed remote arylalkylation of alkenyl amines with excellent regioselectivity and diastereofidelity, involving rare six- or seven-membered metallacycles. This general protocol is compatible with a series of δ- and ε-alkenyl amines, providing corresponding valuable δ,ε- and ε,ζ-difunctionalized aliphatic amines that would be difficult to synthesize. The coordination of the bidentate picolinamide auxiliary and the facile oxidative addition of alkyl halides to Ni(I) species are the key to the success of the developed remote olefin dicarbofunctionalization.
