Allenes as carbon nucleophiles in intramolecular attack on (π-1,3-diene)palladium complexes:: Evidence for trans carbopalladation of the 1,3-diene

被引：29

作者：

Dorange, I ^{[1
]}

Löfstedt, J ^{[1
]}

Närhi, K ^{[1
]}

Franzén, J ^{[1
]}

Bäckvall, JE ^{[1
]}

机构：

[1] Stockholm Univ, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2003年 / 9卷 / 14期

关键词：

C-C coupling; carbopalladation; palladium; reaction mechanisms;

D O I：

10.1002/chem.200305056

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reaction of allene-substituted cyclohexa- and cyclohepta-1,3-dienes with [PdCl2(PhCN)(2)] gave eta(3)-( 1,2,3)-cyclohexenyl- and eta(3)-(1,2,3)-cycloheptenylpalladium complexes. respectively. in which C-C bond formation between the allene and the 1.3-diene has occurred. Analysis of the (pi-allyl)palladium complexes by NMR spectroscopy. using reporter ligands, shows that the C-C bond formation has occurred by a trans carbopalladation involving nucleophilic attack by the middle carbon atom of the allene on a (pi-diene)palladium(n) complex. The stereochemistry of the (pi-allyl)palladium complexes was confirmed by benzoquinone-induced stereoselective transformations to allylic acetates.

引用

页码：3445 / 3449

页数：5

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