Li Pengfei, Kou Guangsheng, Feng Tian, Wang Minyan, Qiu Youai
State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, P. R. China.
Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202311941. doi: 10.1002/anie.202311941. Epub 2023 Sep 25.
Herein, an electrochemically driven NiH-catalyzed reductive coupling of alkyl halides and alkyl alkenes for the construction of Csp -Csp bonds is firstly reported. Notably, alkyl halides serve dual function as coupling substrates and as hydrogen sources to generate NiH species under electrochemical conditions. The tunable nature of this reaction is realized by introducing an intramolecular coordinating group to the substrate, where the product can be easily adjusted to give the desired branched products. The method proceeds under mild conditions, exhibits a broad substrate scope, and affords moderate to excellent yields with over 70 examples, including late-stage modification of natural products and drug derivatives. Mechanistic insights offer evidence for an electrochemically driven coupling process. The sp -carbon-halogen bonds can be activated through single electron transfer (SET) by the nickel catalyst in its low valence state, generated by cathodic reduction, and the generation of NiH species from alkyl halides is pivotal to this transformation.
本文首次报道了一种电化学驱动的镍氢催化的卤代烃与烷基烯烃的还原偶联反应，用于构建Csp -Csp键。值得注意的是，卤代烃在电化学条件下兼具偶联底物和氢源的双重功能，可生成镍氢物种。通过在底物中引入分子内配位基团实现了该反应的可调性，产物可轻松调节以得到所需的支链产物。该方法在温和条件下进行，底物范围广泛，70多个实例的产率适中至优异，包括天然产物和药物衍生物的后期修饰。机理研究为电化学驱动的偶联过程提供了证据。sp -碳-卤键可通过低价态镍催化剂通过阴极还原产生的单电子转移（SET）进行活化，并且从卤代烃生成镍氢物种对该转化至关重要。
