Rhodium‐Catalyzed Dynamic Kinetic Asymmetric Hydrosilylation to Access Silicon‐Stereogenic Center

• DOI: 10.1002/anie.202214147
• Publication Date: 2022-11-04T03:28:33Z
• Authors: Yan Zeng; Xiao‐Jun Fang; Ren‐He Tang; Jing‐Yu Xie; Feng‐Jiao Zhang; Zheng Xu; Yi‐Xue Nie; Li‐Wen Xu
• Keywords: Stereocenter; Desymmetrization; Hydrosilylation; Silanes; Kinetic resolution; Moiety; Chiral ligand

Abstract Strategies on the construction of enantiomerically pure silicon‐stereogenic silanes generally relies desymmetrization prochiral and symmetric substrates. However, dynamic kinetic asymmetric transformations organosilicon compounds have remained underdeveloped unforeseen owing to a lack an effective method for deracemization static silicon stereocenters. Here we report first Rh‐catalyzed intramolecular hydrosilylation (DyKAH) with “silicon‐centered” racemic hydrosilanes that enables facile preparation benzosiloles in good yields excellent enantioselectivities. The special rhodium catalyst controlled by non‐diastereopure‐type mixed phosphine‐phosphoramidite ligand axial chirality multiple stereocenters can induce enantioselectivity efficiently this novel DyKAH reaction. Density functional theory (DFT) calculations suggest amide moiety chiral plays important role facilitating S N 2 substitution chloride ion realize inversion center.