Diverting C–H Annulation Pathways: Nickel-Catalyzed Dehydrogenative Homologation of Aromatic Amides
作者： Zhiqi He , Yong Huang
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摘要: Direct homologation of aromatic amides with internal alkynes has been accomplished via a nickel-catalyzed sequential C–H activation reaction. The use rigid chelating group and strong aprotic polar solvent successfully divert the classical [4 + 2] annulation to [2 2 pathway. This transformation is promoted by simple nickel catalyst without need stoichiometric metal oxidants. Mechanistic studies support an unusual substrate-assisted ligand exchange process. NMR X-ray data suggest [5,5] Ni-bridged metallacycle as resting state. Substrate assisted directing swap plays important role for subsequent meta-C-H insertion. In contrast, can be using bulky, electron-rich phosphine ligand, which favors rapid reductive C–N elimination.
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