The catalytic effect of the NH3 base on the chemical events in the caryolene-forming carbocation cascade

Journal of Computational Chemistry
Daniela E OrtegaAlejandro Toro-Labbé

Abstract

Caryolene formation occur asynchronously in a concerted way through carbocationic rearrangements involving the generation of a secondary or a tertiary carbocation whether the reaction proceeds in the absence or in the presence of NH3 , respectively. Both caryolene formation mechanisms are analyzed within the general framework of the reaction force; the reaction force constant is used to gain insights into the synchronicity of the mechanisms and the reaction electronic flux helps to characterize the electronic activity taking place during the reaction. DFT calculations at the B3LYP/6-31+G(d,p) level show a clear difference in the mechanisms of the base promoted or base free caryolene formation reactions.

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Citations

Sep 9, 2017·Angewandte Chemie·Christopher G NewtonNicolai Cramer
Aug 29, 2018·Physical Chemistry Chemical Physics : PCCP·Daniela E OrtegaAlejandro Toro-Labbé
Mar 25, 2018·Journal of Molecular Modeling·Soledad Gutiérrez-OlivaAlejandro Toro-Labbé

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