A mechanism of addition of a new aromatic electrophile, nitrobenzofuroxan, to cyclopentadiene

The reaction mechanisms of cycloaddition of nitrobenzofuroxan to cyclopentadiene are studied using DFT calculations at the B3LYP/6-31G* level in the gas phase and with account of the solvation effects. The reaction follows a three-step mechanism and includes the formation of a prereaction donor-acce...

Full description

Saved in:
Bibliographic Details
Published inRussian chemical bulletin Vol. 58; no. 8; pp. 1602 - 1608
Main Authors Steglenko, D. V., Kletsky, M. E., Kurbatov, S. V., Minkin, V. I., Goumont, R., Terrier, F.
Format Journal Article
LanguageEnglish
Published Boston Springer US 01.08.2009
Subjects
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Full Articles
Inorganic Chemistry
Organic Chemistry
aromatic electrophiles
polar cycloaddition
reaction indices
nitrobenzofuroxans
[3,3]-sigmatropic rearrangement
density functional theory
quantum chemical calculations
zwitter-ionic σ-complexes
Online AccessGet full text

Cover

More Information
Summary:The reaction mechanisms of cycloaddition of nitrobenzofuroxan to cyclopentadiene are studied using DFT calculations at the B3LYP/6-31G* level in the gas phase and with account of the solvation effects. The reaction follows a three-step mechanism and includes the formation of a prereaction donor-acceptor complex, endo [4+2] cycloaddition with inverse electron demands (IED), and [3,3]-sigmatropic rearrangement to the final endo [2+4] adduct. No formation of stable bipolar σ-complexes on the minimum-energy reaction pathways occurs.
ISSN:1066-5285
1573-9171
DOI:10.1007/s11172-009-0220-2