Computational studies on 3-Aza-Cope rearrangements: protonation-induced switch of mechanism in the reaction of Vinylpropargylamine

Winter, Rainer F.; Rauhut, Guntram

Computational studies on 3-Aza-Cope rearrangements: protonation-induced switch of mechanism in the reaction of Vinylpropargylamine

Dateien

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Datum

2002

Autor:innen

Winter, Rainer F.

Rauhut, Guntram

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Chemistry - A European Journal. 2002, 8(3), pp. 641-649. ISSN 0947-6539. Available under: doi: 10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X

Zusammenfassung

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-ζ 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.

Fachgebiet (DDC)

540 Chemie

Schlagwörter

ab initio calculations, conformation analysis, Cope rearrangement, reactive intermediates, solvent effects

Zitieren

ISO 690

WINTER, Rainer F., Guntram RAUHUT, 2002. Computational studies on 3-Aza-Cope rearrangements: protonation-induced switch of mechanism in the reaction of Vinylpropargylamine. In: Chemistry - A European Journal. 2002, 8(3), pp. 641-649. ISSN 0947-6539. Available under: doi: 10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X

BibTex

@article{Winter2002Compu-13812,
  year={2002},
  doi={10.1002/1521-3765(20020201)8:3<641::AID-CHEM641>3.0.CO;2-X},
  title={Computational studies on 3-Aza-Cope rearrangements: protonation-induced switch of mechanism in the reaction of Vinylpropargylamine},
  number={3},
  volume={8},
  issn={0947-6539},
  journal={Chemistry - A European Journal},
  pages={641--649},
  author={Winter, Rainer F. and Rauhut, Guntram}
}

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