Wang Ruihan, Martínez Sebastián, Schwarzmann Johannes, Zhao Christopher Z, Ramler Jacqueline, Lichtenberg Crispin, Wang Yi-Ming
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Str. 4, 35032 Marburg, Germany.
J Am Chem Soc. 2024 Aug 14;146(32):22122-22128. doi: 10.1021/jacs.4c06235. Epub 2024 Aug 5.
The discovery and utilization of main-group element catalysts that behave similarly to transition metal (TM) complexes have become increasingly active areas of investigation in recent years. Here, we report a series of Lewis acidic bismuth(III) complexes that allow for the catalytic allylic C(sp)-H functionalization of olefins via an organometallic complexation-assisted deprotonation mechanism to generate products containing new C-C bonds. This heretofore unexplored mode of main-group reactivity was applied to the regioselective functionalization of 1,4-dienes and allylbenzene substrates. Experimental and computational mechanistic studies support the key steps of the proposed catalytic cycle, including the intermediacy of elusive Bi-olefin complexes and allylbismuth species.
近年来，发现和利用性能类似于过渡金属（TM）配合物的主族元素催化剂已成为越来越活跃的研究领域。在此，我们报道了一系列路易斯酸性铋（III）配合物，这些配合物可通过有机金属络合辅助去质子化机制实现烯烃的催化烯丙基C(sp)-H官能化，以生成含有新C-C键的产物。这种迄今为止尚未探索的主族反应模式被应用于1,4-二烯和烯丙基苯底物的区域选择性官能化。实验和计算机理研究支持了所提出催化循环的关键步骤，包括难以捉摸的铋-烯烃配合物和烯丙基铋物种的中间体。
