Three BINOL-derived phosphoric acids exhibiting atropisomerism in the 3,3′-positions were obtained by Suzuki coupling reaction. The diastereomeric mixture was resolved by HPLC. Structural assignment was achieved by NOE-NMR analysis and by TD-DFT simulation of the electronic circular dichroism (ECD) spectra. The three atropisomeric catalysts were tested in three enantioselective reactions, comparing their ability to induce enantioselectivity with related, well-known, phosphoric