"Steering Asymmetric Catalysis with Metal-Centered Chirality"CH-640

Over the past few years, our laboratory has advanced the design and application of a novel class of powerful asymmetric catalysts in which the required overall chirality originates solely from a stereogenic metal center (Acc. Chem. Res. 2017, 50, 320; Acc. Chem. Res. 2019, 52, 833. Such chiral-at-metal catalysts are of interest due to their intrinsic structural simplicity (only achiral ligands) and provide untapped opportunities with respect to novel catalyst architectures and properties.
Our initial design consisted of bis-cyclometalated Ir(III) (JACS 2014, 136, 2990) or Rh(III) (Chem. Sci. 2015, 6, 1094) complexes. More recently, we expanded the family of chiral-at-metal catalysts to Ru(II) (JACS 2017, 139, 4322) and Fe(II) (JACS 2019, 141, 4569) bis-(pyridyl-NHC) complexes. Most of these propeller-type complexes feature C₂-symmetry with either L- (left-handed screw) or D-configuration (right-handed screw).
The presentation will provide insight into the design, synthesis, and applications of such chiral-at-metal catalysts including asymmetric photocatalysis (Nature 2014, 515, 100), electrochemistry (Nat. Catal. 2019, 2, 34), and enantioselective C(sp³)-H aminations (Nat. Chem. 2022, 14, 566).