✦ LIBER ✦
Computational Studies on 3-Aza-Cope Rearrangements: Protonation- Induced Switch of Mechanism in the Reaction of Vinylpropargylamine
✍ Scribed by Rainer F. Winter; Guntram Rauhut
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 192 KB
- Volume
- 8
- Category
- Article
- ISSN
- 0947-6539
No coin nor oath required. For personal study only.
✦ Synopsis
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.