Change of Direction: Enantioselective CuH‐Catalyzed 1,2‐Reduction of α,β‐Unsaturated Ketones

Follow diversion: α Substitution in the substrate along with the finely tuned steric and electronic properties of the chiral ligand lead to a complete switch in the regioselectivity of CuH-catalyzed hydrosilylations of unsaturated ketones from the natural 1,4- to a less common 1,2-reaction manifold, as shown by Lipshutz and co-workers (see scheme, DEMS=diethoxymethylsilane).