Highly Regio‐ and Enantioselective Hydrosilylation of gem‐Difluoroalkenes by Nickel Catalysis

The synthesis of small organic molecules with a difluoromethylated stereocenter is particularly attractive in drug discovery. Herein, we have developed an efficient method for the direct generation of difluoromethylated stereocenters through Ni 0 ‐catalyzed regio‐ and enantioselective hydrosilylation of gem ‐difluoroalkenes. The reaction also represents the enantioselective construction of carbon(sp 3 )−silicon bonds with nickel catalysis, which provides an atom‐ and step‐economical synthesis route of high‐value optically active α‐difluoromethylsilanes. This protocol features readily available starting materials and commercial chiral catalysis, broad substrates spanning a range of functional groups with high yield (up to 99 % yield) and excellent enantioselectivity (up to 96 % ee). The enantioenriched products undergo a variety of stereospecific transformations. Preliminary mechanistic studies were performed.