铜催化的硅立体中心苯并硅氧杂环戊二烯的不对称合成。
Copper-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Benzoxasiloles.
作者信息
Gan Wan-Er, Wu Yong-Shun, Wu Bin, Fang Chun-Yuan, Cao Jian, Xu Zheng, Xu Li-Wen
机构信息
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, Hangzhou Normal University, Hangzhou, 311121, Zhejiang, P. R. China.
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, School of Science, Westlake University, P. R. China.
出版信息
Angew Chem Int Ed Engl. 2024 Feb 12;63(7):e202317973. doi: 10.1002/anie.202317973. Epub 2024 Jan 15.
A Cu-catalyzed asymmetric synthesis of silicon-stereogenic benzoxasiloles has been realized via intramolecular Si-O coupling of [2-(hydroxymethyl)phenyl]silanes. Cu(I)/difluorphos is found to be an efficient catalytic system for enantioselective Si-C bond cleavage and Si-O bond formation. In addition, kinetic resolution of racemic substituted [2-(hydroxymethyl)phenyl]silanes using Cu(I)/ PyrOx (pyridine-oxazoline ligands) as the catalytic system is developed to afford carbon- and silicon-stereogenic benzoxasiloles. Ring-opening reactions of chiral benzoxasiloles with organolithiums and Grignard reagents yield various enantioenriched functionalized tetraorganosilanes.
通过[2-(羟甲基)苯基]硅烷的分子内Si-O偶联，实现了铜催化的硅立体中心苯并硅氧杂环戊烷的不对称合成。发现Cu(I)/二氟膦是用于对映选择性Si-C键裂解和Si-O键形成的有效催化体系。此外，还开发了以Cu(I)/PyrOx（吡啶-恶唑啉配体）为催化体系，对外消旋取代的[2-(羟甲基)苯基]硅烷进行动力学拆分，以得到碳和硅立体中心的苯并硅氧杂环戊烷。手性苯并硅氧杂环戊烷与有机锂试剂和格氏试剂的开环反应可生成各种对映体富集的官能化四有机硅烷。
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