title: The catalytic effect of the NH3 base on the chemical events in the caryolene-forming carbocation cascade.
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.
authors.affiliation: Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio De Química Teórica Computacional (QTC), Facultad De Química, Pontificia Universidad Católica De Chile, Casilla 306, Santiago-22, Chile.
authors.forename: Daniela E
authors.initials: DE
authors.lastname: Ortega
authors.affiliation: Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, California, 95616.
authors.forename: Quynh Nhu N
authors.initials: QN
authors.lastname: Nguyen
authors.affiliation: Department of Chemistry, University of California-Davis, 1 Shields Avenue, Davis, California, 95616.
authors.forename: Dean J
authors.initials: DJ
authors.lastname: Tantillo
authors.affiliation: Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio De Química Teórica Computacional (QTC), Facultad De Química, Pontificia Universidad Católica De Chile, Casilla 306, Santiago-22, Chile.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
mesh_terms: D000641:Ammonia / Q000737:chemistry*; D002384:Catalysis; D011789:Quantum Theory
chemical_list: D000641:Ammonia
keywords: carbocation cascade; caryolene formation; reaction elerctronic flux; reaction force; reaction mechanisms