Zhang Ge, Li Yanfei, Wang Ying, Zhang Qian, Xiong Tao, Zhang Qian
Department of Chemistry, Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Northeast Normal University, Changchun, 130024, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2020 Jul 13;59(29):11927-11931. doi: 10.1002/anie.202005341. Epub 2020 May 18.
The catalytic asymmetric creation of silanes with silicon stereocenters is a long-sought but underdeveloped topic, and only a handful of examples have been reported. Moreover, the construction of chiral silanes containing (more than) two stereocenters is a more arduous task and remains unexploited. We herein report an unprecedented copper-catalyzed desymmetrizing protoboration of divinyl-substituted silanes with bis(pinacolato)diboron (B pin ). This method enables the facile preparation of an array of enantiomerically enriched boronate-substituted organosilanes bearing contiguous silicon and carbon stereocenters with exclusive regioselectivity and generally excellent diastereo- and enantioselectivity.
具有硅立体中心的硅烷的催化不对称合成是一个长期以来备受关注但尚未充分发展的课题，目前仅有少数例子被报道。此外，构建含有（超过）两个立体中心的手性硅烷是一项更为艰巨的任务，仍未得到开发。我们在此报告了一种前所未有的铜催化二乙烯基取代硅烷与双（频哪醇合）二硼（Bpin）的去对称化原硼化反应。该方法能够简便地制备一系列对映体富集的硼酸酯取代的有机硅烷，这些硅烷带有相邻的硅和碳立体中心，具有专一的区域选择性以及通常优异的非对映和对映选择性。
