Sampling of Transition States for Predicting Diastereoselectivity Using Automated Search Method-Aqueous
Miho Hatanaka1, Satoshi Maeda2, Keiji Morokuma1
1Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan.
Abstract:
To predict the stereoselectivity of large and flexible reaction systems, structural sampling of many transition states (TSs) is required. We used an automated search method, the artificial force induced reaction (AFIR) method, for TS sampling and found 91 syn- and 73 anti-TSs for the diastereoselective C-C bond formation step of the aqueous lanthanide-catalyzed Mukaiyama aldol reaction. Among them 11 syn- and six anti-TSs are found to contribute significantly to the diastereomeric ratio at room temperature.
Related Concept Videos
Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
Aldol Condensation with β-Diesters: Knoevenagel Condensation
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Base-Catalyzed Aldol Addition Reaction
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration


