Synthesis of Chiral 1,3-Diamines Derived from cis-2-Benzamidocyclohexanecarboxylic Acid and Their Application in the Cu-Catalyzed Enantioselective Henry Reaction

被引：55

作者：

Kodama, Koichi ^{[1
]}

Sugawara, Kazuyuki ^{[1
]}

Hirose, Takuji ^{[1
]}

机构：

[1] Saitama Univ, Grad Sch Sci & Engn, Dept Appl Chem, Sakura Ku, Saitama 3388570, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 48期

关键词：

asymmetric synthesis; chirality; copper; diamines; Henry reaction; OPTICAL RESOLUTION; ALDEHYDES; DERIVATIVES; COMPLEXES; LIGANDS;

D O I：

10.1002/chem.201102136

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In this study, 13 different chiral 1,3-diamines were synthesized from (-)-cis-2-benzamidocyclohexanecarboxylic acid. They were successfully applied as ligands in the Cu-catalyzed asymmetric Henry reaction between benzaldehyde and nitromethane. It was confirmed that the enantioselectivity of the product could be controlled by the substituents on the two amino groups. A time-course study revealed a decrease in product enantioselectivity caused by spontaneous retro-Henry reaction, which was suppressed by conducting the reaction at 0 degrees C. This versatile reaction afforded various beta-nitroalcohols in excellent yields and enantioselectivities (up to 98% yield, 91% enantiomeric excess) under the optimized reaction conditions. The chiral induction mechanism was explained on the basis of a previously proposed transition-state model.

引用

页码：13584 / 13592

页数：9

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