Intramolecular cycloadditions of cyclobutadiene with dienes: experimental and computational studies of the competing (2 + 2) and (4 + 2) modes of reaction.
J Am Chem Soc
; 125(52): 16310-21, 2003 Dec 31.
Article
em En
| MEDLINE
| ID: mdl-14692772
ABSTRACT
Highly functionalized, cyclobutene-containing adducts are afforded through intramolecular cycloadditions between cyclobutadiene and tethered dienes. The cycloaddition displays the following reactivity trend cyclobutadiene serves as a dienophile in intramolecular reactions when it is connected to the diene through a four-atom tether. In cases where a three-atom linker separates the two reaction partners, the cyclobutadiene can function as both a diene and dienophile, affording a mixture of vinylcyclobutane (2 + 2) and cyclohexene-containing cycloadducts (4 + 2). Theoretical studies provide insight into the factors influencing the various pericyclic pathways operative in this system. In cases where cyclobutadiene functions as a diene to generate vinylcyclobutanes, these (2 + 2) adducts can be converted into the corresponding (4 + 2) cyclohexenyl products through a [3,3]-sigmatropic rearrangement.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Ciclobutanos
/
Cicloparafinas
Tipo de estudo:
Prognostic_studies
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2003
Tipo de documento:
Article
País de afiliação:
Estados Unidos