The 3-aza-Cope rearrangements of 3-azoniahexa-1,5-diene (1), 3-azoniahex-1-ene-5-yne (3), and 3-azahex-1-ene-5-yne (5) were investigated up to the coupled-cluster level, CCSD(T), by using a valence triple-zeta basis set. Activation barriers and geometrical parameters of the transition states are provided. Conformational studies were performed for all reactants and products of the reactions. Solvent effects were estimated from self-consistent reaction field calculations. In contrast to the other two species, the Cope rearrangement of 5 was found to proceed by a stepwise mechanism.
%0 Journal Article
%1 ISI:000173750300010
%A Winter, Rainer F.
%A Rauhut, Guntram
%D 2002
%J Chem. - A Eur. J.
%K Ab analysis,Cope theoretische stuttgart chemie effects from:alexanderdenzel rauhut rearrangement,Reactive initio calculations,Conformation intermediates,Solvent theochem
%N 3
%P 641–649
%R 10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X
%T Computational studies on 3-aza-Cope rearrangements: Protonation-induced switch of mechanism in the reaction of vinylpropargylamine
%U http://dx.doi.org/10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X
%V 8
%X The 3-aza-Cope rearrangements of 3-azoniahexa-1,5-diene (1), 3-azoniahex-1-ene-5-yne (3), and 3-azahex-1-ene-5-yne (5) were investigated up to the coupled-cluster level, CCSD(T), by using a valence triple-zeta basis set. Activation barriers and geometrical parameters of the transition states are provided. Conformational studies were performed for all reactants and products of the reactions. Solvent effects were estimated from self-consistent reaction field calculations. In contrast to the other two species, the Cope rearrangement of 5 was found to proceed by a stepwise mechanism.
@article{ISI:000173750300010,
abstract = {The 3-aza-Cope rearrangements of 3-azoniahexa-1,5-diene (1), 3-azoniahex-1-ene-5-yne (3), and 3-azahex-1-ene-5-yne (5) were investigated up to the coupled-cluster level, CCSD(T), by using a valence triple-zeta basis set. Activation barriers and geometrical parameters of the transition states are provided. Conformational studies were performed for all reactants and products of the reactions. Solvent effects were estimated from self-consistent reaction field calculations. In contrast to the other two species, the Cope rearrangement of 5 was found to proceed by a stepwise mechanism.},
added-at = {2019-02-15T17:47:55.000+0100},
author = {Winter, Rainer F. and Rauhut, Guntram},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/27d3d2dd9613cfd97eec4c707bde653f6/theochem},
doi = {10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X},
interhash = {0161b6533033d1d5e00e303ea35c353e},
intrahash = {7d3d2dd9613cfd97eec4c707bde653f6},
issn = {09476539},
journal = {Chem. - A Eur. J.},
keywords = {Ab analysis,Cope theoretische stuttgart chemie effects from:alexanderdenzel rauhut rearrangement,Reactive initio calculations,Conformation intermediates,Solvent theochem},
month = feb,
number = 3,
pages = {641–649},
pmid = {11855711},
timestamp = {2019-02-15T16:47:55.000+0100},
title = {{Computational studies on 3-aza-Cope rearrangements: Protonation-induced switch of mechanism in the reaction of vinylpropargylamine}},
url = {http://dx.doi.org/10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X},
volume = 8,
year = 2002
}
