Regiocontrolled Rh(III)-catalyzed C-C coupling/C-N cyclization mediated by distinctive 1,2-migratory insertion of gem-difluoromethylene allenes: reaction development and mechanistic insight
Regiocontrolled Rh(III)-catalyzed C-C coupling/C-N cyclization mediated by distinctive 1,2-migratory insertion of gem-difluoromethylene allenes: reaction development and mechanistic insight
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DOI：
10.1016/j.cclet.2022.107849
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发表时间：
2022-09
影响因子：
9.1
通讯作者：
Zhi Zhou;Kaifeng Chen;Yi Wang;Xiuhua Zhong;Shuang-zheng Lin;Hui Gao;Wei Yi
中科院分区：
文献类型：
--
作者：
Zhi Zhou;Kaifeng Chen;Yi Wang;Xiuhua Zhong;Shuang-zheng Lin;Hui Gao;Wei Yi
By developinggem‑difluoromethylene allenes as viable partners, regiocontrolled Rh(III)-catalyzed redox-neutral Csingle bondC coupling/Csingle bondN cyclization has been realized to build the pyridin-2(1H)-one motifs with the embedment of aZ-configured monofluoroalkene functionality, in which either (hetero)aromatic or vinylic amides were found to be compatible. Integrated experimental and computational mechanistic studies revealed that a tandem regioselective allene 1,2-insertion/β-H elimination/hydrogen transfer/oxidative addition/cyclization/cis-β-F elimination involving an unconventional Rh(III)-Rh(I)-Rh(III) catalytic cycle accounts for the established transformation. Through further FMO analysis and IGMH maps, a non-covalent weak interaction network between thegem‑difluoromethylene part and the OPiv moiety was rationally defined for the unconventional and specific regioselectivity control.
