Stereopure CF3-substitutedsyn-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 ≥87:13syn/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 SO2region and CH/π
interactions.