Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 74, Issue 18, Pages 6944-6952Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo901109s
Keywords
-
Categories
Funding
- NIH-FIRCA [R03TW007177]
- National Institute of General Medical Sciences
- National Institutes of Health [GM36700]
- Bogazici University Research Fund [09M107]
Ask authors/readers for more resources
Density functional theory calculations were used to investigate the [3,3]- and [1,3]-shifts of O-allylic trichloroacetimidates in the presence of cinchona alkaloids. Thermal [1,3]- and [3,3]-rearrangements proceed through concerted pseudopericyclic transition states to give the corresponding rearranged products. [1,3]-Rearrangement is catalyzed via a double S(N)2' mechanism in which syn addition of the nucleophile is exclusively preferred in both steps. The catalyzed mechanism is favored by a 6.3 kcal/mol free energy difference compared to the alternative [3,3]-rearrangement pathway. The fast-reacting enantiomer is predicted to be determined by the availability of the H-bonding interaction between the catalyst and the substrate.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available