Halogenophilic and classical AdNE mechanisms in nucleophilic vinylic substitution reactions involving the anions of transition metal carbonyls

被引：0
作者：
P. K. Sazonov
G. A. Artamkina
I. P. Beletskaya
机构：
[1] M. V. Lomonosov Moscow State University,
[2] Chemistry Department,undefined
来源：
Theoretical and Experimental Chemistry | 2011年 / 46卷
关键词：
SNV; carbonylate anions; halogenophilic reactions;
D O I：
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摘要：
The mechanism of the reaction of carbonylate anions ([M(CO)nL]–) with highly activated vinyl halides (Hal = Cl, Br, I) was investigated by the method of “anion traps” – the effect of proton donors on the composition of the reaction products. It was demonstrated that the reactions with PhCHal=C(Z)2 (Hal = Br, I;Z=CN, CO2Et) and PhCN=CClI take place through initial attack by the carbonylate at the halogen atom, the reactions with PhCCl=C(CO2Et)2 and PhCOCH=CHHal (Hal = Cl, I) take place through attack by the carbonylate at the π bond (AdNE mechanism), and in the case of E-and Z-PhCN=CHI the two mechanisms operate concurrently. The main laws determining the reaction mechanisms are analyzed.
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页码：350 / 358
页数：8
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