Guo Yonghong, Liu Meng-Meng, Zhu Xujiang, Zhu Liru, He Chuan
Shenzhen Grubbs Institute and Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China.
Angew Chem Int Ed Engl. 2021 Jun 14;60(25):13887-13891. doi: 10.1002/anie.202103748. Epub 2021 May 17.
A Rh-catalyzed asymmetric synthesis of silicon-stereogenic dihydrodibenzosilines featuring axially chiral 6-membered bridged biaryls is demonstrated. In the presence of a Rh catalyst with a chiral diphosphine ligand, a wide range of dihydrodibenzosilines containing both silicon-central and axial chiralities are conveniently constructed in excellent enantioselectivities via dehydrogenative C(sp )-H silylation. Absolute configuration analysis by single-crystal X-ray structures revealed a novel silicon central-to-axial chirality relay phenomenon, which we believe will inspire further research in the field of asymmetric catalysis and chiroptical materials.
展示了一种铑催化的硅立体中心二氢二苯并硅烷的不对称合成，其具有轴向手性的六元桥连联芳基。在具有手性双膦配体的铑催化剂存在下，通过脱氢C(sp )-H硅基化反应，方便地构建了一系列同时含有硅中心手性和轴向手性的二氢二苯并硅烷，且对映选择性优异。通过单晶X射线结构进行的绝对构型分析揭示了一种新型的硅中心到手性轴向的手性传递现象，我们相信这将激发不对称催化和手性光学材料领域的进一步研究。
