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

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] sigmatropi...

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Bibliographic Details
Published in:Tetrahedron 2005-08, Vol.61 (31), p.7359-7365
Main Authors: Arroyo, P., Picher, M.T., Domingo, L.R., Terrier, F.
Format: Article
Language:English
Subjects:
Benzofuroxans
DFT calculations
Electrophilicity
Polar Diels–Alder reactions
Reaction mechanisms
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Summary: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. Graphical Abstract
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2005.05.080