On the Nature of the Oxidative Heterocoupling of Lithium Enolates

被引：63

作者：

Casey, Brian M. ^{[1
]}

Flowers, Robert A., II ^{[1
]}

机构：

[1] Lehigh Univ, Dept Chem, Bethlehem, PA 18015 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 30期

基金：

美国国家卫生研究院;

关键词：

HEXAMETHYLDISILAZIDE-MEDIATED ENOLIZATIONS; DIISOPROPYLAMIDE; REACTIVITY; KETONES; ETHERS; 1,4-DIKETONES; MECHANISMS; COMPLEXES; CHLORIDE; ESTERS;

D O I：

10.1021/ja205017e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The coupling of enolates through single-electron oxidation is one of the most direct routes for generating 1,4-dicarbonyls. Recent work on the intermolecular heterocoupling of equimolar amounts of two different enolates through single-electron oxidation has shown that synthetically useful yields beyond those predicted by statistics can be obtained. To determine the underlying basis for the selective formation of heterocoupled products, kinetic, (7)Li NMR, and synthetic studies were performed. The collection of data obtained from these experiments shows that the selective formation of heterocoupled products is a consequence of heteroaggregation of lithium enolates.

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收藏

页码：11492 / 11495

页数：4

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