Regio‐, Diastereo‐, and Enantioselective Hydrosilylation of Alkyl <i>gem</i> ‐Difluoroalkenes to Construct Carbon and Silicon Stereogenic Centers

Abstract

Abstract The asymmetric hydrofunctionalization of aliphatic alkenes without auxiliary or stabilizing groups presents a significant challenge in modern organic synthesis. We report herein the nickel‐catalyzed enantioselective hydrosilylation of alkyl‐substituted gem ‐difluoroalkenes, which enables the generation of chiral α‐difluoromethylsilanes with excellent regio‐ and enantioselectivity. Moreover, the simultaneous construction of carbon‐ and silicon‐stereogenic centers was achieved with excellent diastereo‐ and enantioselectivity using prochiral silanes. This method provides an efficient approach to access sp 3 ‐enriched C‐stereogenic centers equipped with high‐value difluoromethyl groups. The resulting enantioenriched silanes could undergo a range of stereospecific transformations. Density functional theory (DFT) calculations were performed to elucidate the detailed mechanism.