A DFT study of the polar Diels-Alder reaction between 4-aza-6-nitrobenzofuroxan and cyclopentadiene

被引：59

作者：

Arroyo, P

Picher, MT

Domingo, LR

Terrier, F

机构：

[1] Univ Valencia, Inst Ciencia Mol UIQOT, E-46100 Burjassot, Spain

[2] Univ Versailles, Inst Lavoiser, Lab SIRCOB, CNRS,UMR 8086, F-78035 Versailles, France

来源：

TETRAHEDRON | 2005年 / 61卷 / 31期

关键词：

polar Diels-Alder reactions; benzofuroxans; electrophilicity; reaction mechanisms; DFT calculations;

D O I：

10.1016/j.tet.2005.05.080

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The polar Diels-Alder reaction between 4-aza-6-nitrobenzofuroxan (ANBF) and cyclopentadiene has been studied using DFT procedures at the B3LYP/6-31G* level. Only one highly asynchronous transition state structure associated to the formation of the [4+2] adduct 13 is found. A further [3,3] sigmatropic shift on the [4+2] cycloadduct 13 allows its conversion into the thermodynamically more stable [2+4] cycloadduct 14. The analysis of the global and local electrophilicities of the reagents correctly explain the behaviour of ANBF as a strong electrophile in polar cycloadditions. (c) 2005 Elsevier Ltd. All rights reserved.

引用

页码：7359 / 7365

页数：7

共 45 条

[1]

[Anonymous], 1991, NUCLEOPHILIC AROMATI

[2] The domino reaction between 4,6-dinitrobenzofuroxan and cyclopentadiene. Insights on the nature of the molecular mechanism [J].