Enantioselective Synthesis of P/Si‐Containing Non‐Biaryl Atropisomers with Axial and Point Chirality by Ni‐Catalyzed Silacycloaddition ^†

Comprehensive Summary The catalytic asymmetric synthesis of atropisomers incorporating both axial and central chirality represents an attractive but formidable challenge in synthetic chemistry. We disclose herein a nickel‐catalyzed diastereo‐ and enantioselective silacycloaddition that achieves the atroposelective assembly of multistereogenic aromatic amide‐derived atropisomers. This transformation combines dynamic kinetic resolution of racemic aromatic amide atropisomers with asymmetric Si–C bond activation of benzosilacyclobutenes. Employing chiral BINOL‐derived phosphoramidite ligand featuring chiral cavity of optimal size, this method provides efficient access to a novel class of phosphorus‐containing aromatic amide atropisomers, delivering structurally diverse axially chiral phosphines with concomitant central chirality in good yields, excellent enantioselectivities, and moderate to good diastereoselectivities. This methodology exhibits high configurational stability, as confirmed by both experimental and computational studies, along with remarkable synthetic versatility exemplified by its facile conversion to secondary alcohol‐containing atropisomers via desilylation of such organosilicon compounds. Beyond its immediate utility for constructing modular ligand libraries, this work establishes a transformative platform that promises to inspire phosphine substrate‐compatible asymmetric transformations, addresses long‐standing challenges in the synthesis of stereochemically complex atropisomers, and enables innovative applications across asymmetric catalysis and related fields.