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
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
收藏
页码:3445 / 3449
页数:5
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