Hydrogen-Bonding Ability of Noyori–Ikariya Catalysts Enables Stereoselective Access to CF₃-Substituted syn-1,2-Diols via Dynamic Kinetic Resolution

Abstract

Stereopure CF3-substituted syn-1,2-diols were prepared via the reductive dynamic kinetic resolution of the corresponding racemic α-hydroxyketones in HCO2H/Et3N. (Het)aryl, benzyl, vinyl, and alkyl ketones are tolerated, delivering products with ≥95% ee and ≥87:13 syn/anti. 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 SO2 region and CH/π interactions.

Penta- versus hexa-coordinated iridium catalysts control the reactivity of the direct reductive amination between aliphatic amines and aliphatic ketones: a DFT-guided mechanism

“…16–23 This is particularly advantageous for homogeneous metal-catalysed reactions involving gaseous reagents such as H 2 , CO, CO 2 , and others, which are routinely employed in hydrogenations, hydroformylations, (alkoxy)carbonylations, carboxylations and related ones, including also the asymmetric variants. 24–39…”