Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of thi...Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.展开更多
基金supported by the National Natural Science Foundation of China(No.21702119)Natural Science Foundation of Shandong Province(Nos.ZR2016JL012,ZR2020JQ07)the Scientific Research Foundation of Qingdao University of Science and Technology(No.1203043003457)。
文摘Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.
