Ambident Reactivity of Imidazolium Cations as Evidence of the Dynamic Nature of N-Heterocyclic Carbene-Mediated Organocatalysis

被引：10
|
作者：
Galkin, Konstantin I. [1 ]
Karlinskii, Bogdan Ya. [1 ]
Kostyukovich, Alexander Yu. [1 ]
Gordeev, Evgeniy G. [1 ]
Ananikov, Valentine P. [1 ]
机构：
[1] Russian Acad Sci, ND Zelinsky Inst Organ Chem, Leninsky Prospect 47, Moscow 119991, Russia
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2020年 / 26卷 / 39期
关键词：
abnormal" carbenes; carbanionic carbenes; density functional calculations; N-heterocyclic carbenes; organocatalysis; ACETATE IONIC LIQUIDS; COORDINATION CHEMISTRY; COOPERATIVE CATALYSIS; NHC; ACTIVATION; UMPOLUNG; NUCLEOPHILICITY; COMPLEXES; MECHANISM; REMOTE;
D O I：
10.1002/chem.201905704
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
This work reveals ambident nucleophilic reactivity of imidazolium cations towards carbonyl compounds at the C2 or C4 carbene centers depending on the steric properties of the substrates and reaction conditions. Such an adaptive behavior indicates the dynamic nature of organocatalysis proceeding via a covalent interaction of imidazolium carbenes with carbonyl substrates and can be explained by generation of the H-bonded ditopic carbanionic carbenes.
引用
收藏
页码：8567 / 8571
页数：5
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