Defining effective chiral binding sites at lanthanides - highly enantioselective reagents and catalysts from binaphtholate and pybox ligands

被引：40

作者：

Aspinall, HC ^{[1
]}

Greeves, N ^{[1
]}

机构：

[1] Univ Liverpool, Dept Chem, Donnan & Robert Robinson Labs, Liverpool L69 7ZD, Merseyside, England

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 647卷 / 1-2期

基金：

英国工程与自然科学研究理事会;

关键词：

binaphthol; catalysis; cyanohydrin; enantioselective synthesis; lanthanide; pybox;

D O I：

10.1016/S0022-328X(01)01370-5

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

This paper reviews our work with enantioselective lanthanide reagents and catalysts for organic synthesis. Heterometallic reagents M-3[Ln(binol)(3)] (M = Li; Ln = lanthanide; H(2)binol = binaphthol) mediate the addition of RLi to aldehydes with ee's of up to 84%. Structural studies have been carried out where M = Li or Na, Ln = Eu, Y or Yb and with enantiomerically pure or racemic binol. There are important differences in coordination chemistry dependent on the ionic radius of M and Ln. [LnCl(3)(pybox)(2)] are effective catalysts for the silylcyanation of aldehydes, giving ee's of up to 89% under convenient reaction conditions. Structural studies have been undertaken on [Ln(OTf)(3)(Pr'-pybox)(2)] for Ln = La, Eu or Yb. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：151 / 157

页数：7