Density functional theory study of the cycloaddition reaction of furan derivatives with masked o-benzoquinones. Does the furan act as a dienophile in the cycloaddition reaction?
J Org Chem
; 67(3): 959-65, 2002 Feb 08.
Article
em En
| MEDLINE
| ID: mdl-11856044
ABSTRACT
The molecular mechanism for the cycloaddition reaction between 2-methylfuran and a masked o-benzoquinone has been characterized using quantum mechanical calculations at the B3LYP/6-31G theory level. An analysis of the results on the reaction pathway shows that the reaction takes place along a polar stepwise mechanism. The first and rate-determining step corresponds to the nucleophilic attack of the furan ring on the doubly conjugated position of the 2,4-dienone system present at the masked o-benzoquinone to give a zwitterionic intermediate. Closure of this intermediate affords the formally [2 + 4] cycloadduct. For the second step two reactive channels have been characterized corresponding to the formation of the formally [2 + 4] and [4 + 2] cycloadducts. Analysis of the energetic results indicates that while the first is the meta regiocontrolling and endo stereocontrolling step, the second one is responsible for the formation of the unexpected formally [2 + 4] cycloadduct. The global and local electrophilicity/nucleophilicity power of the reactants and intermediate have been evaluated to rationalize these results. Density functional theory analysis for these cycloadditions is in complete agreement with the experimental outcome, explaining the reactivity and selectivity of the formation of the formally [2 + 4] cycloadducts.
Buscar no Google
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Ano de publicação:
2002
Tipo de documento:
Article
País de afiliação:
Espanha