The role of asynchronous bond formation in the diastereoselective epoxidation of cyclic enol ethers: a density functional theory study.
Density functional theory (DFT) (Becke3LYP functional and the D95 basis set) was used to study the influence of substitution on the dimethyldioxirane epoxidation reaction of six- and seven-membered cyclic enol ethers. In agreement with our previously reported experimental results, the calculations predict that substitution on the cyclic enol ether influences the level of diastereoselectivity. Apparent only from the calculations is that the degree of synchronicity in the transition state is important in the diastereoselectivity.
Orendt
Anita M
AM
Department of Chemistry, 315 South 1400 East, University of Utah, Salt Lake City, Utah 84112-0850, USA. anita.orendt@utah.edu
Roberts
Scott W
SW
Rainier
Jon D
JD
D003500:Cyclization; D004852:Epoxy Compounds / Q000138:chemical synthesis / Q000737:chemistry; D004988:Ethers, Cyclic / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010082:Oxepins / Q000138:chemical synthesis / Q000737:chemistry; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
D004852:Epoxy Compounds; D004988:Ethers, Cyclic; D010082:Oxepins; D011714:Pyrans