Catalytic Synthesis of a Chiral Silicon Center

手性硅中心的催化合成

• 批准号: 24655078
• 负责人: TOBISU Mamoru
• 金额: $ 2.58万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Challenging Exploratory Research
• 财政年份: 2012
• 资助国家: 日本
• 起止时间: 2012-04-01 至 2013-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-24655078/
• 关键词: キラルケイ素; 触媒反応; 不斉ケイ素中心; キラルケイ素中心

Chemistry of chiral silicon centers remain unexplored, when compared to that of chiral carbon centers, mainly due to the lack of methods for the construction of chiral silicon centers. The purpose of this study is to develop a catalytic method for the generation of chiral silicon centers on the basis of rhodium-catalyzed synthesis of benzosiloles, which we reported previously. We found that the substrate containing an isopropyldimethylsilyl group was employed, a less bulky methyl group is cleaved exclusively, and enantioselective cleavage of two enantiotopic methyl groups was possible by adding a chiral phosphine ligand to form a benzosilole bearing a chiral silicon center.

与手性碳中心的化学相比，手性硅中心的化学仍然未被探索，主要是由于缺乏用于构建手性硅中心的方法。本研究的目的是发展一种在铑催化合成苯并硅杂环戊二烯的基础上生成手性硅中心的催化方法。我们发现，含有异丙基二甲基甲硅烷基的基板被采用，一个体积较小的甲基被专门切割，和两个对映异构的甲基的对映选择性裂解是可能的，通过添加手性膦配体形成苯并噻咯轴承手性硅中心。

项目成果

Rhodium-Catalyzed Carbon-Silicon Bond Activation for Synthesis of Benzosilole Derivatives

• DOI: 10.1021/ja3096174
• 发表时间: 2012-11-28
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Onoe, Masahiro;Baba, Katsuaki;Chatani, Naoto
• 通讯作者: Chatani, Naoto