A DFT study of the Huisgen 1,3-dipolar cycloaddition between hindered thiocarbonyl ylides and tetracyanoethylene

被引：63

作者：

Domingo, LR ^{[1
]}

Picher, MT ^{[1
]}

机构：

[1] Univ Valencia, Inst Ciencia Mol, Dept Quim Organ, E-46100 Burjassot, Spain

来源：

TETRAHEDRON | 2004年 / 60卷 / 23期

关键词：

D O I：

10.1016/j.tet.2004.04.024

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism for the 1,3-dipolar cycloaddition between the hindered thiocarbonyl ylide 1 and tetracyanoethylene 2 has been studied at the B3LYP/6-31 G* level. Formation of the [3+2] cycloadduct 4 takes place through a stepwise mechanism that is initiated by the nucleophilic attack of the thiocarbonyl ylide I to the ethylene derivative 2 to give a zwitterionic intermediate IN. The subsequent cyclization of IN yields a seven-membered cyclic ketene imine 6, which equilibrates with the thermodynamically more stable [3+2] cycloadduct 4. The computed free energies are in agreement with the experimental outcomes. (C) 2004 Elsevier Ltd. All rights reserved.

引用

页码：5053 / 5058

页数：6

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