Rearrangement of propargylic esters:: Metal-based stereospecific synthesis of (E)- and (Z)-Knoevenagel derivatives

被引：77

作者：

Barluenga, Jose ^{[1
]}

Riesgo, Lorena ^{[1
]}

Vicente, Ruben ^{[1
]}

Lopez, Luis A. ^{[1
]}

Tomas, Miguel ^{[1
]}

机构：

[1] Univ Oviedo, Inst Univ Quim Organometalica Enrique Moles, Unidad Asociada CSIC, E-33071 Oviedo, Spain

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 25期

关键词：

D O I：

10.1021/ja072864r

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Alkoxy-substituted propargylic esters undergo regioselective 1,3-acyloxy migration in the presence of Pt(II) and Cu(I) catalysts, allowing the preparation of alpha-ylidene-beta-keto and -malonate esters. The reaction proved to also be stereodivergent as the Pt(II) and the Cu(I) catalysts perform the isomerization with complementary Z/E selectivity. Moreover, alkynyl-conjugated Knoevenagel products are produced from (bisalkynyl)methyl acetates. In such a case, the reaction is chemoselective as the 1,3-acetyl migration takes place through the alkoxyalkyne group in preference over the phenylalkyne group. The resulting (E)-alkynylenone unit suffers metal-catalyzed cyclization into the furyl ring, generating a copper(I) carbene species.

引用

页码：7772 / +

页数：3

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