American Chemical Society
ol9b00633_si_001.pdf (1.84 MB)

C–H Acidity and Arene Nucleophilicity as Orthogonal Control of Chemoselectivity in Dual C–H Bond Activation

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journal contribution
posted on 2019-03-20, 20:05 authored by Ji-Ren Liu, Ye-Qing Duan, Shuo-Qing Zhang, Lu-Jing Zhu, Yuan-Ye Jiang, Siwei Bi, Xin Hong
We discovered a cooperative gold/silver catalysis mechanism in the oxidative cross-coupling reaction between 1,2,4,5-tetrafluorobenzene and N-TIPS-indole, using DFT calculations. A silver­(I)-catalyzed CMD mechanism is responsible for the C–H activation of 1,2,4,5-tetrafluorobenzene, and C–H acidity determines the chemoselectivity. A gold­(III)-catalyzed SE2Ar mechanism is responsible for the C3–H activation of N-TIPS-indole, and arene nucleophilicity determines the chemo- and regioselectivity. The orthogonal chemoselectivity control provides a mechanistic guide for dual C–H activation reactions.