99646-05-6Relevant articles and documents
GAS-PHASE ACID-INDUCED RING OPENING IN SUBSTITUTED 1,2-EPOXYCYCLOHEXANES
Crotti, Paolo,Macchia, Franco,Pizzabiocca, Adriano,Renzi, Gabriele,Speranza, Maurizio
, p. 739 - 746 (2007/10/02)
The nature and the stereoisomeric distribution of the neutral products obtained from the gas-phase attack of radiolytically formed Broensted +, CH5+, C2H5+, and t-C4H9+> and Lewis +, t-C4H9+, and CH3FCH3+> acids on several substituted 1,2-epoxycyclohexanes have been investigated under different experimental conditions.Isolation and identification of the neutral substituted products allowed us to confirm previous indications about highly regio- and stereo-selective cationic nucleophilic displacements on these substrates occuring in the gas-phase with complete inversion of the configuration at the reaction centre (the α-C atom).In some cases, extensive acid-induced isomerization became the only observable pathway.The relative extent of the competiting substitution and isomerization was found to depend on several factors, including the structural features and internal energy of the oxonium derivative of the epoxy substrate.The results obtained from the present gas-phase experiments are discussed in relation to gas-phase and solution studies.