通过施加应变策略实现硅烷的亲核活化以生成功能性硅芳族化合物。
Nucleophilic Activation of Hydrosilanes via a Strain-Imposing Strategy Leading to Functional Sila-aromatics.
作者信息
Ikeuchi Toshiya, Hirano Keiichi, Uchiyama Masanobu
机构信息
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Cluster of Pioneering Research (CPR), Advanced Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama 351-0198, Japan.
出版信息
J Am Chem Soc. 2021 Apr 7;143(13):4879-4885. doi: 10.1021/jacs.0c12619. Epub 2021 Mar 5.
Carefully designed cyclic hydrosilanes enable -selective hydrosilylation of unactivated alkynes without transition metal catalysts via silicate formation. Employment of sterically demanding bidentate ligands of silicon increases steric congestion upon silicate formation, and this strain-imposing strategy facilitates hydride transfer. This hydrosilylation provides efficient access to diverse benzosiloles, silaphenalenes, and related silacycles.
精心设计的环状硅烷能够通过硅酸盐的形成，在无过渡金属催化剂的情况下实现未活化炔烃的 - 选择性硅氢化反应。使用空间位阻较大的硅双齿配体会增加硅酸盐形成时的空间拥挤，这种施加应变的策略促进了氢化物转移。这种硅氢化反应为合成各种苯并硅杂环戊二烯、硅杂菲以及相关的硅杂环提供了有效途径。
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