Distal Ionic Substrate–Catalyst Interactions Enable Long-Range Stereocontrol: Access to Remote Quaternary Stereocenters through a Desymmetrizing Suzuki–Miyaura Reaction

[Image: see text] Spatial distancing of a substrate’s reactive group and nonreactive catalyst-binding group from its pro-stereogenic element presents substantial hurdles in asymmetric catalysis. In this context, we report a desymmetrizing Suzuki–Miyaura reaction that establishes chirality at a remote quaternary carbon. The anionic, chiral catalyst exerts stereocontrol through electrostatic steering of substrates, even as the substrate’s reactive group and charged catalyst-binding group become increasingly distanced. This study demonstrates that precise long-range stereocontrol is achievable by engaging ionic substrate–ligand interactions at a distal position.