Nickel-Catalyzed Enantio- and Diastereoselective Synthesis of Fluorine-Containing Vicinal Stereogenic Centers

The construction
of fluorinated architectures has been a topic
of interest to medicinal chemists due to their unique ability to improve
the pharmacokinetic properties of bioactive compounds. However, the
stereoselective synthesis of fluoro-organic compounds with vicinal
stereogenic centers is a challenge. Herein, we present a directing-groupfree
nickel-hydride catalyzed hydroalkylation of fluoroalkenes to afford
fluorinated motifs with two adjacent chiral centers in excellent yields
and stereoselectivities. Our method provides expedient access to biologically
relevant, highly enantioenriched organofluorine compounds. Furthermore,
the strategy can be used for the diastereo- and enantioselective synthesis
of vicinal difluorides, which have recently gained attention in the
fields of organocatalysis and peptide mimics.