Origins of Selectivity and General Model for Chiral Phosphoric Acid-Catalyzed Oxetane Desymmetrizations.

The origins of the high enantioselectivity of chiral phosphoric acid-catalyzed oxetane desymmetrizations were investigated by density functional theory (DFT) calculations. Distortion of the catalyst structure, caused by steric crowding in the catalyst pocket of one enantiomeric transition state, is...

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Detalles Bibliográficos
Publicado en:Journal of the American Chemical Society Vol. 138; no. 38; pp. 12356 - 12360
Autores principales: Champagne, Pier Alexandre, Houk, K. N.
Formato: Artículo
Publicado: American Chemical Society 9/28/2016
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Acceso en línea:Ver este registro en EBSCOhost
Descripción
Sumario:The origins of the high enantioselectivity of chiral phosphoric acid-catalyzed oxetane desymmetrizations were investigated by density functional theory (DFT) calculations. Distortion of the catalyst structure, caused by steric crowding in the catalyst pocket of one enantiomeric transition state, is the main cause for stereochemical preference. A general model was developed to assist in the rational design of new catalysts for related transformations.