%0 Journal Article
%T Caryolene-forming carbocation rearrangements
%A Quynh Nhu N. Nguyen
%A Dean J. Tantillo
%J Beilstein Journal of Organic Chemistry
%D 2013
%I 
%R 10.3762/bjoc.9.37
%X Density functional theory calculations on mechanisms of the formation of caryolene, a putative biosynthetic precursor to caryol-1(11)-en-10-ol, reveal two mechanisms for caryolene formation: one involves a base-catalyzed deprotonation/reprotonation sequence and tertiary carbocation minimum, whereas the other (with a higher energy barrier) involves intramolecular proton transfer and the generation of a secondary carbocation minimum and a hydrogen-bridged minimum. Both mechanisms are predicted to involve concerted suprafacial/suprafacial [2 + 2] cycloadditions, whose asynchronicity allows them to avoid the constraints of orbital symmetry.
%K carbocation
%K cycloaddition
%K density functional theory
%K mechanism
%K reactive intermediates
%K terpene
%U http://dx.doi.org/10.3762/bjoc.9.37