Wang Xiaohong, He Xiaochun, Zhang Xuemei, Wang Qingqing, Huang Qian, Qu Ruiling, Lian Zhong
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, Chengdu, 610041, China.
Nat Commun. 2025 Jun 4;16(1):5200. doi: 10.1038/s41467-025-60459-0.
Mechanical-force-induced redox catalysis has emerged as a green and expeditous approach in synthetic chemistry, relying on single-electron transfer from polarized piezoelectric materials to substrates initiated by mechanical agitation. However, the piezoelectric potential generated can sometimes be insufficient to activate the electron transfer process, similar to the limitations observed in photocatalytic reactions. In this work, we introduce a catalytic strategy employing a consecutive mechanical-force-induced electron transfer (ConMET) strategy. This strategy uses piezoelectric materials as mechanochemical redox catalysts with 9-phenyl-dihydroacridine as a sacrificial electron donor, enabling efficient consecutive electron transfer. Our method effectively reduces aryl iodides, bromides, and even electron-rich aryl chlorides, which possess reduction potentials as high as -2.8 V (vs. SCE), leading to the formation of aryl radicals. Ultimately, this strategy facilitates anti-Markovnikov hydroarylation of alkenes and dehalogenative deuteration of aromatic halides under mild conditions.
机械力诱导的氧化还原催化已成为合成化学中一种绿色且快速的方法，它依赖于通过机械搅拌引发的从极化压电材料到底物的单电子转移。然而，所产生的压电势有时可能不足以激活电子转移过程，这与光催化反应中观察到的局限性类似。在这项工作中，我们引入了一种采用连续机械力诱导电子转移（ConMET）策略的催化方法。该策略使用压电材料作为机械化学氧化还原催化剂，以9-苯基-二氢吖啶作为牺牲电子供体，实现高效的连续电子转移。我们的方法能有效还原芳基碘化物、溴化物，甚至是还原电位高达-2.8 V（相对于饱和甘汞电极）的富电子芳基氯化物，从而形成芳基自由基。最终，该策略在温和条件下促进了烯烃的反马氏氢芳基化反应以及芳基卤化物的脱卤氘代反应。
