Cage‐Shaped Phosphites Having C3‐Symmetric Chiral Environment: Steric Control of Lewis Basicity and Application as Chiral Ligands in Rhodium‐Catalyzed Conjugate Additions

Designing chiral ligands with an axial symmetry higher than C2-rotational symmetry is one of the most crucial approaches to improving enantioselectivity in asymmetric synthesis. Herein, we report C3-symmetric chiral cage-shaped phosphites. Their Lewis basicity and chiral environment are precisely controlled by the tethered group. The cage-shaped phosphites successfully worked as chiral ligands in Rh-catalyzed asymmetric conjugate additions, realizing acceptable yields with excellent enantioselectivity, and were used to synthesize a pharmacologically important molecule.