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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.

SUBMITTER: Schneebeli ST

PROVIDER: S-EPMC2766528 | biostudies-literature | 2009 Mar

REPOSITORIES: biostudies-literature

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Quantitative DFT modeling of the enantiomeric excess for dioxirane-catalyzed epoxidations.

Schneebeli Severin T ST Hall Michelle Lynn ML Breslow Ronald R Friesner Richard R

Journal of the American Chemical Society 20090301 11

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 ...[more]

PMID: 19243187

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