Modeling of Solvolysis Reaction Mechanism for Cation-Olefin Cyclizations

Abstract

We report on a computational study of cation-olefin cyclization mechanism under solvolytic conditions. The combined explicit-continuum solvent model aimed at providing a complete estimate of media effects is used to investigate the nature, stability, and conformational behavior of cationic species involved in the reaction. The comparison between the explicit-continuum and leaving group models is also provided. Our study of reactionpath ways shows that protonated cyclopropane is the key intermediate on the potential energy surface of cation-olefin cyclizations.

Keywords

• Ab initio
• Carbocations
• Cation-olefin cyclizations
• Molecular modeling
• Solvent effects