通过质谱筛选发现的用于酮不对称硅氢化反应的新型催化剂。

New catalysts for the asymmetric hydrosilylation of ketones discovered by mass spectrometry screening.

作者信息

Yao Sulan, Meng Jun-Cai, Siuzdak Gary, Finn M G

机构信息

Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.

出版信息

J Org Chem. 2003 Apr 4;68(7):2540-6. doi: 10.1021/jo026365e.

DOI:10.1021/jo026365e

PMID:12662022

Abstract

A method for determining enantiomeric excess by mass spectrometry was employed to screen a family of chiral phosphite P,N-ligands for activity in the rhodium-catalyzed asymmetric hydrosilylation of ketones. The identification of an effective set of ligands was followed by preliminary studies of the reaction scope and mechanism. Asymmetric induction of 84-88% ee for larger-scale reactions was observed, which is close to the level of the best alternative catalysts previously discovered. The screening method was shown to be applicable to a variety of substrates without the need for special optimization.

摘要

采用一种通过质谱法测定对映体过量的方法，来筛选一类手性亚磷酸酯P,N-配体，以考察其在铑催化的酮不对称硅氢化反应中的活性。在鉴定出一组有效的配体之后，对反应范围和机理进行了初步研究。观察到大规模反应的对映体选择性为84 - 88% ee，这接近先前发现的最佳替代催化剂的水平。结果表明，该筛选方法适用于多种底物，无需进行特殊优化。