Zhou Huan, Fan Li-Wen, Ren Yang-Qing, Wang Li-Lei, Yang Chang-Jiang, Gu Qiang-Shuai, Li Zhong-Liang, Liu Xin-Yuan
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, 518055, China.
School of Science and Institute of Scientific Research, Great Bay University, Dongguan, 523000, China.
Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202218523. doi: 10.1002/anie.202218523. Epub 2023 Feb 16.
The copper-catalyzed enantioselective radical difunctionalization of alkenes from readily available alkyl halides and organophosphorus reagents possessing a P-H bond provides an appealing approach for the synthesis of α-chiral alkyl phosphorus compounds. The major challenge arises from the easy generation of a P-centered radical from the P-H-type reagent and its facile addition to the terminal side of alkenes, leading to reverse chemoselectivity. We herein disclose a radical 1,2-carbophosphonylation of styrenes in a highly chemo- and enantioselective manner. The key to the success lies in not only the implementation of dialkyl phosphites with a strong bond dissociation energy to promote the desired chemoselectivity but also the utilization of an anionic chiral N,N,N-ligand to forge the chiral C(sp )-P bond. The developed Cu/N,N,N-ligand catalyst has enriched our library of single-electron transfer catalysts in the enantioselective radical transformations.
从易得的卤代烷烃和具有P-H键的有机磷试剂出发，通过铜催化的烯烃对映选择性自由基双官能团化反应，为合成α-手性烷基磷化合物提供了一种有吸引力的方法。主要挑战在于容易从P-H型试剂生成以磷为中心的自由基，以及它容易加成到烯烃的末端，导致化学选择性反转。我们在此公开了一种以高度化学和对映选择性方式进行的苯乙烯自由基1,2-碳膦酰化反应。成功的关键不仅在于使用具有高键解离能的亚磷酸二烷基酯来促进所需的化学选择性，还在于利用阴离子手性N,N,N-配体来构建手性C(sp³)-P键。所开发的Cu/N,N,N-配体催化剂丰富了我们在对映选择性自由基转化中的单电子转移催化剂库。
