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

作　　者：Ting Liu Xiangqing Feng Haifeng Du 

机构地区：[1]Beijing National Laboratory for Molecular Sciences,CAS Key Laboratory of Molecular Recognition and Function,Institute of Chemistry,Chinese Academy of Sciences,Beijing,100190 China [2]University of Chinese Academy of Sciences,Beijing,100049 China

出　　处：《Chinese Journal of Chemistry》2024年第8期853-857,共5页中国化学（英文版）

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

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.

关 键 词：Asymmetric catalysis HYDROSILYLATION Ketones Frustrated Lewis pairs Chiral boranes 

分 类 号：O62[理学—有机化学]