Enantioselective, cyclopentene-forming annulations via NHC-catalyzed benzoin-oxy-cope reactions

被引：270

作者：

Chiang, Pei-Chen ^{[1
]}

Kaeobamrung, Juthanat ^{[1
]}

Bode, Jeffrey W. ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 12期

关键词：

H ACTIVATION/COPE REARRANGEMENT; DIELS-ALDER REACTIONS; ALPHA; BETA-UNSATURATED ALDEHYDES; STEREOSELECTIVE-SYNTHESIS; GAMMA-BUTYROLACTONES; FUNCTIONALIZED CYCLOPENTENES; ACTIVATED CARBOXYLATES; NUCLEOPHILIC CARBENES; CONJUGATE ADDITION; ENALS;

D O I：

10.1021/ja0705543

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral N-heterocyclic carbene catalysts generated from triazolium salts promote the cyclopentene-forming annulation of alpha,beta-unsaturated aldehydes and 4-oxoenoates with excellent levels of enantioinduction and preference for the cis-1,3,4-trisubstituted cyclopentene diastereomer. Although the observed products could arise by conjugate additions of catalytically generated homoenolates, our mechanistic and stereochemical investigations strongly support a novel reaction manifold featuring an intermolecular crossed-benzoin reaction and an NHC-catalyzed oxy-Cope rearrangement.

引用

页码：3520 / +

页数：3

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