title: Quantitative DFT modeling of the enantiomeric excess for dioxirane-catalyzed epoxidations.
abstract: Herein we report the first fully quantum mechanical study of enantioselectivity for a large data set. We show that transition state modeling at the UB3LYP-DFT/6-31G* level of theory can accurately model enantioselectivity for various dioxirane-catalyzed asymmetric epoxidations. All the synthetically useful high selectivities are successfully "predicted" by this method. Our results hint at the utility of this method to further model other asymmetric reactions and facilitate the discovery process for the experimental organic chemist. Our work suggests the possibility of using computational methods not simply to explain organic phenomena, but also to predict them quantitatively.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Severin T
authors.initials: ST
authors.lastname: Schneebeli
authors.forename: Michelle Lynn
authors.initials: ML
authors.lastname: Hall
authors.forename: Ronald
authors.initials: R
authors.lastname: Breslow
authors.forename: Richard
authors.initials: R
authors.lastname: Friesner
mesh_terms: D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry*; D008958:Models, Molecular; D055601:Organic Chemistry Phenomena; D011789:Quantum Theory
chemical_list: D004852:Epoxy Compounds; C061799:dioxirane