由非外消旋联苯双膦配体络合的氢化铜催化的芳基酮的不对称硅氢化反应。

Asymmetric hydrosilylation of aryl ketones catalyzed by copper hydride complexed by nonracemic biphenyl bis-phosphine ligands.

作者信息

Lipshutz Bruce H, Noson Kevin, Chrisman Will, Lower Asher

机构信息

Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.

出版信息

J Am Chem Soc. 2003 Jul 23;125(29):8779-89. doi: 10.1021/ja021391f.

DOI:10.1021/ja021391f

PMID:12862472

Abstract

When complexed by selected ligands in either the BIPHEP or the SEGPHOS series, CuH is an extremely reactive catalyst capable of effecting asymmetric hydrosilylations of aromatic ketones at temperatures between -50 and -78 degrees C. Inexpensive silanes serve as stoichiometric sources of hydride. Substrate-to-ligand ratios exceeding 100000:1 have been documented. The level of induction is usually in the >90% ee category. The nature of the reagent has been investigated using spectroscopic and chemical means, although its composition remains unclear.

摘要

当与BIPHEP或SEGPHOS系列中的特定配体络合时，氢化铜是一种极具活性的催化剂，能够在-50至-78摄氏度的温度下实现芳香酮的不对称硅氢化反应。廉价的硅烷用作化学计量的氢化物来源。已记录底物与配体的比例超过100000:1。诱导水平通常在>90% ee的范围内。尽管其组成仍不清楚，但已使用光谱和化学方法对该试剂的性质进行了研究。