Chiral PSiSi‐Ligand Enabled Iridium‐Catalyzed Atroposelective Intermolecular C−H Silylation

Abstract Catalytic enantioselective intermolecular C−H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, a new type of chiral silyl ligand is developed, which enables the first iridium‐catalyzed atroposelective intermolecular C−H silylation reaction of 2‐arylisoquinolines. This protocol features mild reaction conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, 99 % ee ), delivering enantioenriched axially chiral silane platform molecules with facile convertibility. Key to the success of this unprecedented transformation relies on a novel chiral PSiSi‐ligand, which facilitates the intermolecular C−H silylation process with perfect chem‐, regio‐ and stereo‐control via a multi‐coordinated silyl iridium complex.