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Zhang, Zuxiao; Zhang, Xin; Nagib, David A. (, Chem)null (Ed.)
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Nakafuku, Kohki M.; Zhang, Zuxiao; Wappes, Ethan A.; Stateman, Leah M.; Chen, Andrew D.; Nagib, David A. (, Nature Chemistry)null (Ed.)
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Zhang, Zuxiao; Stateman, Leah M.; Nagib, David A. (, Chemical Science)null (Ed.)A Cu-catalyzed strategy has been developed that harnesses a radical relay mechanism to intercept a distal C-centered radical for C–C bond formation. This approach enables selective δ C–H (hetero)arylation of sulfonamides via intramolecular hydrogen atom transfer (HAT) by an N-centered radical. The radical relay is both initiated and terminated by a Cu catalyst, which enables incorporation of arenes and heteroarenes by cross-coupling with boronic acids. The broad scope and utility of this catalytic method for δ C–H arylation is shown, along with mechanistic probes for selectivity of the HAT mechanism. A catalytic, asymmetric variant is also presented, as well as a method for accessing 1,1-diaryl-pyrrolidines via iterative δ C–H functionalizations.more » « less
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