Experimental investigation into the mechanism of the epoxidation of aldehydes with sulfur ylides.
A mechanistic study of the epoxidation of aldehydes with sulfur ylides has been carried out. The DeltaG++ of the reaction was determined to be 22.2 kcal/mol at 298 K. A 13C kinetic isotope effect was determined to be 1.026 for the carbonyl carbon of benzaldehyde. A secondary deuterium isotope effect was determined to be 0.93 for the aldehydic hydrogen atom of benzaldehyde. Substituent effects on reaction rate were studied, and a Hammett rho of +2.50 was found.
Edwards
David R
DR
Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, ON, Canada K7M 3N6. cruddenc@chem.queensu.ca
Montoya-Peleaz
Pedro
P
Crudden
Cathleen M
CM