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Abstract
The generation of alkyl radical from C(sp3)−H substrates via hydrogen atom abstraction represents a desirable yet underexplored strategy in alkylation reaction since involving common concerns remain adequately unaddressed, such as the harsh reaction conditions, limited substrate scope, and the employment of noble metal- or photo-catalysts and stoichiometric oxidants. Here, we utilize the synergistic strategy of photoredox and hydrogen atom transfer (HAT) catalysis to accomplish a general and practical functionalization of unactived C(sp3)−H centers with broad reaction scope, high functional group compatibility, and operational simplicity. A combination of validation experiments and density functional theory reveals that the N-centered radicals, generated from free N − H bond in a stepwise electron/proton transfer event, are the key intermediates that enable an intramolecular 1,5-HAT or intermolecular HAT process for nucleophilic carbon-centered radicals formation to achieve heteroarylation, alkylation, amination, cyanation, azidation, trifluoromethylthiolation, halogenation and deuteration. The practical value of this protocol is further demonstrated by the gram-scale synthesis and the late-stage functionalization of natural products and drug derivatives.
Hydrogen atom abstraction from C(sp3)−H substrates for the generation of alkyl radical represents an underexplored strategy in alkylation reactions. Here the authors describe the synergistic utilization of photoredox and hydrogen atom transfer catalysis to accomplish a general and practical functionalization of unactived C(sp3)−H centers.
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1 Zhejiang University of Technology, Key Laboratory for Green Pharmaceutical Technologies and Related Equipment of Ministry of Education, College of Pharmaceutical Sciences, Hangzhou, P. R. of China (GRID:grid.469325.f) (ISNI:0000 0004 1761 325X)
2 Zhejiang University of Technology, Key Laboratory for Green Pharmaceutical Technologies and Related Equipment of Ministry of Education, College of Pharmaceutical Sciences, Hangzhou, P. R. of China (GRID:grid.469325.f) (ISNI:0000 0004 1761 325X); Zhejiang University of Technology, Taizhou Key Laboratory of Advanced Manufacturing Technology, Taizhou Institute, Taizhou, P. R. of China (GRID:grid.469325.f) (ISNI:0000 0004 1761 325X)