The first azacyclopentenyl carbinyl radical isomerizations (ACCRI): independent use of steric and electronic (polarization) effects as gating elements.
J Am Chem Soc
; 125(24): 7266-71, 2003 Jun 18.
Article
em En
| MEDLINE
| ID: mdl-12797800
ABSTRACT
The first examples of the azacyclopentenyl carbinyl radical isomerization are described within a series of enantiomerically enriched 2-substituted indolines, a substructure found extensively in both heterocyclic and natural product chemistry. The isomerization was identified by the varying loss of enantiomeric enrichment (ee) of imines during aryl radical cyclizations to azomethine nitrogen. Independent modification of the steric and electronic nature of the ring substituents revealed the full spectrum of sensitivity to these variables and ultimately defined the use of these effects as gating elements. An example is also given in which a 1,4-amino group transfer is effected via the isomerization mechanism. Analogies are drawn between the title isomerization and the azacyclopropyl carbinyl radical isomerization that has been studied in both chemical and biological contexts.
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Base de dados:
MEDLINE
Assunto principal:
Compostos Aza
/
Ciclopentanos
/
Indóis
Tipo de estudo:
Prognostic_studies
Idioma:
En
Ano de publicação:
2003
Tipo de documento:
Article