Dynamic Kinetic Asymmetric Cross-Benzoin Additions of β-Stereogenic α-Keto Esters

被引：64

作者：

Goodman, C. Guy ^{[1
]}

Johnson, Jeffrey S. ^{[1
]}

机构：

[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2014年 / 136卷 / 42期

关键词：

N-HETEROCYCLIC CARBENES; HETEROATOM-SUBSTITUTED ALDEHYDES; C BOND FORMATION; ENANTIOSELECTIVE SYNTHESIS; ACYLOIN CONDENSATIONS; CATALYZED-REACTIONS; TRIAZOLIUM SALTS; RESOLUTION; ACID; TRANSFORMATIONS;

D O I：

10.1021/ja508521a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The dynamic kinetic resolution of beta-halo a-keto esters via an asymmetric cross-benzoin reaction is described. A chiral N-heterocyclic carbene catalyzes the umpolung addition of aldehydes to racemic a-keto esters. The resulting fully substituted beta-halo glycolic ester products are obtained with high levels of enantio- and diastereocontrol. The high chemoselectivity observed is a result of greater electrophilicity of the a-keto ester toward the Breslow intermediate. The reaction products are shown to undergo highly diastereoselective substrate-controlled reduction to give highly functionalized stereotriads.

引用

页码：14698 / 14701

页数：4

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