State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.
Angew Chem Int Ed Engl. 2020 Apr 16;59(16):6555-6560. doi: 10.1002/anie.201914740. Epub 2020 Feb 25.
Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through-space metal/hydrogen shifts allow functionalization of C-H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5-palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl-, benzyl-, and borylsilanes, constituting a unique C(sp )-H transformation based on a 1,5-palladium migration process.
有机硅化合物在工业和学术界都得到了广泛的应用。对各种有机硅烷的合成研究非常有吸引力。通过空间的金属/氢键迁移允许在远程位置对 C-H 键进行功能化，否则这很难实现。然而，到目前为止，似乎还没有报道芳基到烷基 1,5-钯迁移过程。本文报道了通过空间的硅上甲基的烯烃化、芳基化和硼化反应来制备各种乙烯基、苄基和硼基硅烷，这是一种基于 1,5-钯迁移过程的独特的 C(sp3)-H 转化。
