Studies on the bisoxazoline- and (-)-sparteine-mediated enantioselective addition of organolithium reagents to imines

被引：26

作者：

Denmark, Scott E. ^{[1
]}

Nakajima, Noriyuki ^{[1
]}

Stiff, Cory M. ^{[1
]}

Nicaise, Olivier J. -C. ^{[1
]}

Kranz, Michael ^{[1
]}

机构：

[1] Univ Illinois, Dept Chem, Roger Adams Lab 245, Urbana, IL 61801 USA

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2008年 / 350卷 / 7-8期

关键词：

aldimines; bisoxazolines; catalysis; enantioselective addition; organolithium reagents;

D O I：

10.1002/adsc.200800017

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The enantioselective addition of organolithium reagents to N-anisylaldimines promoted by chiral bisoxazolines and (-)-sparteine as external ligands is described. This reaction proceeds readily with a wide range of aldimine substrates (aliphatic, aromatic, olefinic) and organolithium nucleophiles (Me, n-Bu, Ph, vinyl) in excellent yields (81-99%) and with high enantioselectivities (up to 97:3.0 er). The external ligands can be used in substoichiometric amounts albeit with slightly attenuated enantioselectivities. A systematic evaluation of the structural features of the bisoxazolines revealed a primary contribution from the substituent at C(4) and a secondary influence from the bridging substituents. A computational analysis (PM3) provided a clear rationalization for the origin of enantioselectivity.

引用

页码：1023 / 1045

页数：23

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