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非活化环丙烷的温和开环1,3-硼氢化反应

Mild Ring-Opening 1,3-Hydroborations of Non-Activated Cyclopropanes.

作者信息

Wang Di, Xue Xiao-Song, Houk Kendall N, Shi Zhuangzhi

机构信息

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.

Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, 90095, USA.

出版信息

Angew Chem Int Ed Engl. 2018 Dec 17;57(51):16861-16865. doi: 10.1002/anie.201811036. Epub 2018 Nov 21.

Abstract

The Brown hydroboration reaction, first reported in 1957, is the addition of B-H across an olefin in an anti-Markovnikov fashion. Here, we solved a long-standing problem on mild 1,3-hydroborations of non-activated cyclopropanes. A three-component system including cyclopropanes, boron halides, and hydrosilanes has been developed for borylative ring-opening of cyclopropanes following the anti-Markovnikov rule, under mild reaction conditions. Density functional theory (M06-2X) calculations show that the preferred pathway involves a cationic boron intermediate which is quenched by hydride transfer from the silane.

摘要

布朗硼氢化反应于1957年首次报道,是硼氢键以反马氏规则加成到烯烃上。在此,我们解决了一个长期存在的关于非活化环丙烷温和1,3-硼氢化反应的问题。已开发出一种包括环丙烷、卤化硼和硅烷的三组分体系,用于在温和反应条件下按照反马氏规则进行环丙烷的硼化开环反应。密度泛函理论(M06-2X)计算表明,优选的反应途径涉及一个阳离子硼中间体,该中间体通过硅烷的氢转移淬灭。

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