通过碳-碳活化实现的烯烃1,1-插入反应实现无张力酮的分子内单碳同系化反应。
Intramolecular One-Carbon Homologation of Unstrained Ketones via C-C Activation-Enabled 1,1-Insertion of Alkenes.
作者信息
Huang Jiangkun, Zhang Rui, Wu Xiuli, Dong Guangbin, Xia Ying
机构信息
West China School of Public Health and West China Fourth Hospital, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China.
Department of Chemistry, University of Chicago, Chicago 60637, United States.
出版信息
Org Lett. 2022 Apr 1;24(12):2436-2440. doi: 10.1021/acs.orglett.2c00716. Epub 2022 Mar 18.
Here, we describe the development of a Rh-catalyzed intramolecular one-carbon homologation of unstrained aryl ketones through a formal 1,1-insertion process of olefins, enabled by temporary directing group (TDG)-aided C-C activation. The reaction provides a distinct approach to access various substituted 1-indanones. Computational mechanistic studies reveal that the formal 1,1-insertion is realized by a selective C(sp)-C(sp) activation and turnover limiting 2,1-insertion into the alkene, followed by a facile β-H elimination and reinsertion process.
在此，我们描述了一种通过烯烃的形式上的1,1-插入过程实现的、由临时导向基团（TDG）辅助的C-C活化所促成的Rh催化的无张力芳基酮分子内单碳同系化反应。该反应为获得各种取代的1-茚酮提供了一种独特的方法。计算机理研究表明，形式上的1,1-插入是通过选择性的C(sp)-C(sp)活化以及限速的2,1-插入到烯烃中实现的，随后是一个容易的β-H消除和再插入过程。
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