Huang Yu-Hao, Wu Yichen, Zhu Zile, Zheng Sujuan, Ye Zihang, Peng Qian, Wang Peng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
State Key Laboratory and Institute of Elemento-Organic Chemistry and Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, P. R. China.
Angew Chem Int Ed Engl. 2022 Jan 3;61(1):e202113052. doi: 10.1002/anie.202113052. Epub 2021 Nov 23.
Enantiopure monohydrosilanes are versatile chiral reagents for alcohol resolution and mechanistic investigation. Herein, we have demonstrated the asymmetric synthesis of monohydrosilanes via an intramolecular hydrosilylation strategy. This protocol is suitable for the synthesis of five- and six-membered cyclic monohydrosilanes, including a class of chiral oxasilacycles, with excellent diastereo-, regio-, and enantioselectivities. Notably, the catalyst loading could be reduced to 0.1 mol % which makes this one of the most efficient methods to access chiral monohydrosilanes. Mechanistic studies and DFT calculations indicate this Rh-catalyzed intramolecular asymmetric hydrosilylation reaction might proceed via a Chalk-Harrod mechanism, and the enantio-determining step was predicted to be oxidative addition of Si-H bond.
对映体纯的单氢硅烷是用于醇拆分和机理研究的通用手性试剂。在此，我们展示了通过分子内硅氢化策略不对称合成单氢硅烷。该方法适用于合成五元及六元环状单氢硅烷，包括一类手性氧杂硅杂环，具有优异的非对映、区域和对映选择性。值得注意的是，催化剂负载量可降至0.1 mol%，这使其成为获得手性单氢硅烷最有效的方法之一。机理研究和密度泛函理论计算表明，这种铑催化的分子内不对称硅氢化反应可能通过查尔克-哈罗德机理进行，并且对映体决定步骤预计为Si-H键的氧化加成。
