The nature and stereoisomeric distribution of neutral products obtained from the gas-phase attack of radiolytically formed Broensted and Lewis acids on substituted 1,2-epoxycyclohexanes were studied under different exptl. conditions. Highly regio- and stereoselective cationic nucleophilic displacements, with complete inversion of configuration at the reaction center, were obsd. In some cases, extensive acid-induced isomerization became the only observable pathway. The relative extent of competing substitution and isomerization depend on several factors, including the structure features and internal-energy excess of the oxonium derivs. of the epoxy substrates.
GAS-PHASE ACID-INDUCED RING-OPENING IN SUBSTITUTED 1,2-EPOXYCYCLOHEXANES / P., Crotti; F., Macchia; A., Pizzabiocca; G., Renzi; Speranza, Maurizio. - In: GAZZETTA CHIMICA ITALIANA. - ISSN 0016-5603. - STAMPA. - 117:(1987), pp. 739-745.
GAS-PHASE ACID-INDUCED RING-OPENING IN SUBSTITUTED 1,2-EPOXYCYCLOHEXANES
SPERANZA, Maurizio
1987
Abstract
The nature and stereoisomeric distribution of neutral products obtained from the gas-phase attack of radiolytically formed Broensted and Lewis acids on substituted 1,2-epoxycyclohexanes were studied under different exptl. conditions. Highly regio- and stereoselective cationic nucleophilic displacements, with complete inversion of configuration at the reaction center, were obsd. In some cases, extensive acid-induced isomerization became the only observable pathway. The relative extent of competing substitution and isomerization depend on several factors, including the structure features and internal-energy excess of the oxonium derivs. of the epoxy substrates.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.