Organic syntheses via transition-metal complexes.: 119.: α-Methylenation and α-alkenylation of α,β-unsaturated amides by means of carbene tungsten complexes:: A novel Baylis-Hillman type reaction

被引：10

作者：

Aumann, R ^{[1
]}

Fu, XL ^{[1
]}

Holst, C ^{[1
]}

Fröhlich, R ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 21期

关键词：

D O I：

10.1021/om020392d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Fischer carbene complexes were found to undergo Baylis-Hillman type additions to alpha,beta-unsaturated acid amides. Reactions of (non-CH-acidic) carbene tungsten complexes la-c with (CH-acidic) but-2-enoic acid amides 2 in the presence of POCl3/Et3N resulted in an alpha-addition of the carbene ligand to the amide backbone and formation of cross-conjugated aminocarbene complexes 3. Reaction of CH-acidic carbene tungsten complexes 1d-h gave the cross-conjugated aminocarbene complexes 9 (which are double-bond isomers of compounds 3) together with (cyclobutenyl)carbene complexes 10, by alpha- and beta-addition, respectively, to the but-2-enoic amides 2. Compounds 9 and 10 are valence isomers, but they do not interconvert thermally.

引用

页码：4356 / 4368

页数：13

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