ORGN 685 |
| Recently, a new diastereoselective reaction resulting in an N-hydroxy alkyl lactam was discovered. The starting materials, a hydroxy alkyl azide and a substituted cyclohexanone, form a hemiketal. The azide then attacks the carbonyl carbon giving an intramolecular Schmidt reaction. This process has the potential to be an important tool for synthesis. Thus, we have used ab initio calculations to explore the stereoselectivity of this modified Schmidt reaction. A preference for the N2+ leaving group to be in an axial position and the stabilization of this cation by an axial phenyl group was observed for the heterosubstituted cyclohexane intermediate. Results concerning the effect of solvent on our calculations and the effect of phenyl substituents on the cation-π interaction will be presented. Preliminary calculations on the mechanism of the Schmidt reaction will also be discussed. |
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Physical Organic Chemistry: Calculations, Mechanisms, Photochemistry, and High-Energy Species
1:00 PM-5:00 PM, Wednesday, 16 March 2005 Convention Center -- Room 11A, Oral
Division of Organic Chemistry |