期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 74, 期 18, 页码 6944-6952出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo901109s
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资金
- NIH-FIRCA [R03TW007177]
- National Institute of General Medical Sciences
- National Institutes of Health [GM36700]
- Bogazici University Research Fund [09M107]
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.
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