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

共 35 条

[1]

Barluenga J, 2001, ANGEW CHEM INT EDIT, V40, P3392, DOI 10.1002/1521-3773(20010917)40:18<3392::AID-ANIE3392>3.0.CO

[2]

2-Y

[3] Tandem PtCl2 catalyzed-thermal [3,3] rearrangements of enyne acetates [J].

Cariou, K ;

Mainetti, E ;

Fensterbank, L ;

Malacria, M .

TETRAHEDRON, 2004, 60 (43) :9745-9755

[4] Olefination of ketones using a gold(III)-catalyzed Meyer-Schuster rearrangement [J].

Engel, Douglas A. ;

Dudley, Gregory B. .

ORGANIC LETTERS, 2006, 8 (18) :4027-4029

[5]

Fehr, 2006, ANGEW CHEM, V118, P2967

[6] Copper-catalyzed cycloisomerizations of 5-En-1-yn-3-ols [J].

Fehr, C ;

Farris, I ;

Sommer, H .

ORGANIC LETTERS, 2006, 8 (09) :1839-1841

[7] Synthesis of (-)-cubebol by face-selective platinum-, gold-, or copper-catalyzed cycloisomerization: Evidence for chirality transfer [J].

Fehr, Charles ;

Galindo, Jose .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (18) :2901-2904

[8] Catalytic carbophilic activation:: Catalysis by platinum and gold π acids [J].

Fuerstner, Alois ;

Davies, Paul W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (19) :3410-3449

[9] Platinum- and gold-catalyzed rearrangement reactions of propargyl acetates:: Total syntheses of (-)-α-cubebene, (-)-cubebol, sesquicarene and related terpenes [J].

Fürstner, A ;

Hannen, P .

CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (11) :3006-3019

[10] A "hard/soft" mismatch enables catalytic Friedel-Crafts acylations [J].

Fürstner, A ;

Voigtländer, D ;

Schrader, W ;

Giebel, D ;

Reetz, MT .

ORGANIC LETTERS, 2001, 3 (03) :417-420

← 1 2 3 4 →