Chen Ke, Zhu Hongdan, Jiang Shuxin, Ding Kuiling, Peng Qian, Wang Xiaoming
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, P. R. China.
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, P. R. China.
Nat Commun. 2025 Mar 30;16(1):3077. doi: 10.1038/s41467-025-58398-x.
Mono-metallic catalysts dominate in homogeneous catalysis, wherein all the element steps generally occur on one metal site. Inspired from bimetallic active sites in both enzymes and heterogeneous catalysts, the development of binuclear catalysis can offer the potential to induce novel intermediates, reactivity, and selectivity. Metal-catalyzed hydroarylation of alkynes generally leads to one alkyne incorporated products and alkyne dimerization-hydrocarbofunctionalization is rather challenging via conventional mono-metallic intermediates. Herein, a highly selective dimerization-hydrocarbofunctionalization of internal alkynes is achieved via dinickel catalysis, leading to the formation of synthetically challenging pentasubstituted 1,3-dienes. Mechanistic studies suggest that each Ni site can promote distinct elementary steps of two alkynes to generate a di-vinyl di-Ni intermediate. Such a mode of "binuclear convergent catalysis" is fundamentally different from the traditional mono-metallic catalysis and may provide new understanding on binuclear synergistic effects at atomic and molecular level.
单金属催化剂在均相催化中占主导地位，其中所有的基元步骤通常发生在一个金属位点上。受酶和多相催化剂中双金属活性位点的启发，双核催化的发展有望诱导产生新型中间体、反应活性和选择性。金属催化的炔烃氢芳基化反应通常生成含一个炔烃的产物，而通过传统的单金属中间体实现炔烃二聚-烃基官能团化则颇具挑战性。在此，通过二镍催化实现了内炔烃的高选择性二聚-烃基官能团化反应，生成了具有合成挑战性的五取代1,3-二烯。机理研究表明，每个镍位点可促进两个炔烃的不同基元步骤，生成二乙烯基二镍中间体。这种“双核收敛催化”模式与传统的单金属催化有根本区别，可能为原子和分子水平上的双核协同效应提供新的认识。
