Ligand-Accelerated Direct C−H Arylation of BINOL: A Rapid One-Step Synthesis of Racemic 3,3′-Diaryl BINOLs

An ortho‐selective rhodium‐catalyzed direct C−H arylation of 1,1′‐bi‐2‐naphthol (BINOL), to deliver the widely used but not easily available 3,3′‐diaryl BINOL, has been developed. This highly efficient one‐step synthetic approach is the shortest route to date and is greatly facilitated by the newly developed ligand system comprising tBu2PCl, Ph2‐cod, and Cy3P⋅HBF4. In addition, the same procedure can facilitate the challenging syntheses of 3‐bulkyaryl BINOLs in good to excellent yields. System anew: An ortho‐selective rhodium‐catalyzed direct C−H arylation of 1,1′‐bi‐2‐naphthol (BINOL), to deliver the widely used 3,3′‐diaryl BINOL, has been developed. This highly efficient one‐step synthetic approach is facilitated by the newly developed ligand system comprising tBu2PCl, Ph2‐cod, and Cy3P⋅HBF4. In addition, the same procedure can facilitate the syntheses of 3‐bulkyaryl BINOLs in good to excellent yields. cod= 1,5‐cyclooctadiene.