Hydrogen-Bonding Ability of Noyori-Ikariya Catalysts Enables Stereoselective Access to CF-Substituted -1,2-Diols via Dynamic Kinetic Resolution.

Stereopure CF-substituted -1,2-diols were prepared via the reductive dynamic kinetic resolution of the corresponding racemic α-hydroxyketones in HCOH/EtN. (Het)aryl, benzyl, vinyl, and alkyl ketones are tolerated, delivering products with ≥95% ee and ≥87:13 /. This methodology offers rapid access to stereopure bioactive molecules. Furthermore, DFT calculations for three types of Noyori-Ikariya ruthenium catalysts were performed to show their general ability of directing stereoselectivity via the hydrogen bond acceptor SO region and CH/π interactions.