Exploiting Self‐Assembly for Ligand‐Scaffold Optimization: Substrate‐Tailored Ligands for Efficient Catalytic Asymmetric Hydroboration

Mix and match: A self-assembled ligand library (SAL XY) affords a wide range of R/S ratios in Rh-catalyzed asymmetric hydroboration (see scheme; nbd=2,5-norbornadiene, R* is a chiral substituent). Ligand-scaffold optimization reveals “substrate-tailored” ligands that afford high regio- and enantioselectivity for a variety of ortho-substituted styrene derivatives.