Application of the chiral poisoning strategy: Enantioselective Diels-Alder catalysis with a racemic Ru/BINAP-monoxide Lewis acid

被引：34

作者：

Faller, JW ^{[1
]}

Lavoie, AR ^{[1
]}

Grimmond, BJ ^{[1
]}

机构：

[1] Yale Univ, Dept Chem, New Haven, CT 06511 USA

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 08期

关键词：

D O I：

10.1021/om011052f

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A chiral poisoning strategy has been applied to the catalyst system for the asymmetric Diels-Alder reaction between methacrolein and cyclopentadiene to produce enantioenriched exo-2-methylbicyclo[2.2.1]hept-5-ene-2-carboxaldehyde. When 1 was mixed with AgSbF6, the dicationic Lewis acid [(+/-)-p-cymeneRu-(H2O)(BINPO)](SbF6)(2) (+/-2) was generated. The additions of a number of chiral poisons (P* enantiopure ligand) were found to deactivate one of the enantiomers of the catalyst with varied levels of selectivity. The most effective chiral poison was either L-proline or L-prolinamide. In catalytic trials with L-proline, an ee of up to 54% was observed. In the case where a stoichiometric amount of (+/-)-Ru/methacrolein reacted in the presence of L-prolinamide, the DA product was obtained with ee = 60% (S), de = 96% (exo), and 92% conversion.

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页码：1662 / 1666

页数：5

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