Development of a Formal [4+1] Cycloaddition: Pd(OAc)2-Catalyzed Intramolecular Cyclopropanation of 1,3-Dienyl β-Keto Esters and MgI2-Promoted Vinylcyclopropane-Cyclopentene Rearrangement

被引：70
|
作者：
Coscia, Rockford W. [1 ]
Lambert, Tristan H. [1 ]
机构：
[1] Columbia Univ, Dept Chem, New York, NY 10027 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 07期
关键词：
ALPHA; BETA-UNSATURATED CARBONYL-COMPOUNDS; STEREOSELECTIVE-SYNTHESIS; BOND FORMATION; PALLADIUM; CYCLIZATION; ANNULATION; DIENES; CARBOCYCLIZATION; 1,4-OXIDATION; DERIVATIVES;
D O I：
10.1021/ja809226x
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A formal [4 + 1] cycloaddition of 1,3-dienyl beta-keto esters has been developed. This two step process involves Pd(II)-catalyzed intramolecular cyclopropanation to produce vinylcyclopropanes and a subsequent mild vinylcyclopropane-cyclopentene rearrangement promoted by MgI2. The cyclopropanation method notably requires the use Of Mg(ClO4)(2), presumably to facilitate keto-enol tautomerization, and is greatly improved by the use of copper(II) isobutyrate as co-oxidant. A range of substrates with various substitution patterns is demonstrated.
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页码：2496 / +
页数：4
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