Asymmetric Partial Hydrosilylation of 2,2-Difluoro-1,3-diketones with Chiral Frustrated Lewis Pairs

作     者：Ting Liu Xiangqing Feng Haifeng Du Ting Liu;Xiangqing Feng;Haifeng Du

作者机构：Beijing National Laboratory for Molecular SciencesCAS Key Laboratory of Molecular Recognition and FunctionInstitute of ChemistryChinese Academy of SciencesBeijing100190 China University of Chinese Academy of SciencesBeijing100049 China 

出 版 物：《Chinese Journal of Chemistry》 (中国化学（英文版）)

年 卷 期：2024年第42卷第8期

页      面：853-857页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：the financial support from the National Natural Science Foundation of China(21825108 and 22331011) 

主　　题：Asymmetric catalysis Hydrosilylation Ketones Frustrated Lewis pairs Chiral boranes 

摘      要：Comprehensive Summary,The asymmetric partial reduction of 1,3-diketones stands as a straightforward pathway to access optically active β-hydroxyketones. In this paper, an asymmetric Piers-type hydrosilylation of 2,2-difluoro-1,3-diketones was successfully realized by using a frustrated Lewis pair of chiral borane and tricyclohexylphosphine as a catalyst, delivering a variety of α,α-difluoro-β-hydroxyketones in high yields with up to 99% ee. Significantly, no over-reduced diol products were observed even with an excess amount of silanes. The product can be conveniently converted to α,α-difluoro-β-hydroxyester or 1,3-anti-diol via an oxidation with m-CPBA or a reduction with DIBAL-H without obvious loss of ee.