Department of Chemistry, University of Minnesota─Twin Cities, Minneapolis, Minnesota 55455, United States.
Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, United States.
J Am Chem Soc. 2022 Jan 12;144(1):86-92. doi: 10.1021/jacs.1c11503. Epub 2021 Dec 13.
The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated" C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.
将重氮化合物插入苄基溴代物的“非活化”C-C 键中，这是一项具有挑战性的工作，也是当前研究的热点。在此，我们报告了一种简单的路易斯酸催化的反应，可实现该过程。该同系化反应通过苯翁离子中间体进行，产物中含有苄基季碳中心和可进一步衍生化的烷基溴。计算分析为反应机制提供了重要的见解，特别是关键的选择性决定步骤。
