Mechanically planar chiral rotaxanes through catalytic desymmetrization

•Unprecedented desymmetrization strategy for creating mechanically planar chirality •High enantioselectivity across a diverse range of interlocking bonds •New class of anionic chiral ligands for asymmetric catalysis •Long-range stereocontrol enabled by distal electrostatic interactions Establishing mechanical chirality has remained a substantial synthetic hurdle despite the fast-growing applications of interlocked architectures in supramolecular chemistry. Here, we report the development of a catalyst-controlled desymmetrization strategy that decouples the creation of mechanically planar chirality and assembly of interlocked bonds. Employing a novel class of anionic chiral phosphine ligands, the Pd-catalyzed Suzuki-Miyaura reactions enable enantioselective access to various mechanically planar chiral rotaxanes. This study demonstrates that precise catalytic stereocontrol over mechanical chirality is achievable by engaging distal ionic substrate-catalyst interactions, despite the noncovalent nature of the interlocking stereogenic elements. Establishing mechanical chirality has remained a substantial synthetic hurdle despite the fast-growing applications of interlocked architectures in supramolecular chemistry. Here, we report the development of a catalyst-controlled desymmetrization strategy that decouples the creation of mechanically planar chirality and assembly of interlocked bonds. Employing a novel class of anionic chiral phosphine ligands, the Pd-catalyzed Suzuki-Miyaura reactions enable enantioselective access to various mechanically planar chiral rotaxanes. This study demonstrates that precise catalytic stereocontrol over mechanical chirality is achievable by engaging distal ionic substrate-catalyst interactions, despite the noncovalent nature of the interlocking stereogenic elements.