INTERMEDIATES IN THE PALLADIUM-CATALYZED REACTION OF 1,3-DIENES .8. THE REACTION OF PALLADIUM BUTADIENE COMPLEXES WITH ETHYL METHYLACETOACETATE

被引：25

作者：

DOHRING, A ^{[1
]}

GODDARD, R ^{[1
]}

HOPP, G ^{[1
]}

JOLLY, PW ^{[1
]}

KOKEL, N ^{[1
]}

KRUGER, C ^{[1
]}

机构：

[1] MAX PLANCK INST KOHLENFORSCH,D-45466 MULHEIM,GERMANY

来源：

INORGANICA CHIMICA ACTA | 1994年 / 222卷 / 1-2期

关键词：

CRYSTAL STRUCTURES; CATALYSIS; DIENE COMPLEXES; PALLADIUM COMPLEXES; METHYLACETOACETATE COMPLEXES;

D O I：

10.1016/0020-1693(94)03907-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The catalytic reaction of 1,3-butadiene with ethyl methylacetoacetate in the presence of (eta2-1,3-butadiene)Pd(R2P(CH2)(n)PR2) compounds has been investigated. The product is a mixture of 1:1 adducts and the rate of reaction is highest when n = 2, R = Pr(i) and in dichloromethane as solvent. Insight into the mechanism has been obtained by studying the stoichiometric reaction of (eta2-1,3-butadiene)Pd(Pr2(i)PC2H4PPr2i) with the ester using variable temperature NMR spectroscopy and it has been shown that initially an [(eta3-1-MeC3H4)-Pd(Pr2(i)PC2H4PPr2i)]+ species is formed which reacts further to give (eta2-alkene)Pd(Pr2(i)PC2H4PPr2i) compounds in which the product of the catalysis is complexed to the palladium atom. The crystal structures of three side products, viz. Pd2(Pr2(i)PCH2PPr2i)2, [eta1,eta3-C8H12)Pd]2(Me2PC2H4PMe2) and ClCH2Pd(Cy2PC2H4PCy2)Cl, have been determined by X-ray diffraction.

引用

页码：179 / 192

页数：14

共 36 条

[1] STEREOCHEMISTRY AND MECHANISM OF NICKEL-CATALYZED HYDROCYANATION OF OLEFINS AND CONJUGATED DIENES [J].