Tang Man, Zhu Wenyan, Sun Huaxing, Wang Jing, Jing Su, Wang Minyan, Shi Zhuangzhi, Hu Jiefeng
School of Chemistry and Molecular Engineering, Nanjing Tech University Nanjing 211816 China
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210023 China.
Chem Sci. 2023 Jun 13;14(26):7355-7360. doi: 10.1039/d3sc02461j. eCollection 2023 Jul 5.
Methods to efficiently synthesize organosilanes are valuable in the fields of synthetic chemistry and materials science. During the past decades, boron conversion has become a generic and powerful approach for constructing carbon-carbon and other carbon-heteroatom bonds, but its potential application in forming carbon-silicon remains unexplored. Herein, we describe an alkoxide base-promoted deborylative silylation of benzylic organoboronates, geminal bis(boronates) or alkyltriboronates, allowing for straightforward access to synthetically valuable organosilanes. This selective deborylative methodology exhibits operational simplicity, broad substrate scope, excellent functional group compatibility and convenient scalability, providing an effective and complementary platform for the generation of diversified benzyl silanes and silylboronates. Detailed experimental results and calculated studies revealed an unusual mechanistic feature of this C-Si bond formation.
高效合成有机硅烷的方法在合成化学和材料科学领域具有重要价值。在过去几十年中，硼转化已成为构建碳-碳键和其他碳-杂原子键的通用且强大的方法，但其在形成碳-硅键方面的潜在应用仍未得到探索。在此，我们描述了一种醇盐碱促进的苄基有机硼酸酯、偕二硼酸酯或烷基三硼酸酯的脱硼硅基化反应，可直接获得具有合成价值的有机硅烷。这种选择性脱硼方法操作简单、底物范围广、官能团兼容性好且易于放大，为生成多样化的苄基硅烷和硅硼酸酯提供了一个有效且互补的平台。详细的实验结果和计算研究揭示了这种碳-硅键形成的不寻常机理特征。
