Premium
The catalytic effect of the NH 3 base on the chemical events in the caryolene‐forming carbocation cascade
Author(s) -
Ortega Daniela E.,
Nguyen Quynh Nhu N.,
Tantillo Dean J.,
ToroLabbé Alejandro
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24294
Subject(s) - carbocation , chemistry , cascade , catalysis , base (topology) , synchronicity , cascade reaction , computational chemistry , chemical reaction , reaction mechanism , photochemistry , organic chemistry , mathematical analysis , philosophy , mathematics , chromatography , epistemology
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 NH 3 , 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. © 2016 Wiley Periodicals, Inc.