Synthesis of Chiral‐Bridged Atropisomeric Monophosphine Ligands with Tunable Dihedral Angles and their Applications in Asymmetric Suzuki–Miyaura Coupling Reactions

Precise chiral recognition was firstly realized in the construction of diastereomeric biaryl monophosphines by means of the substrate‐directed asymmetric annulation reactions. A series of new chiral‐bridged atropisomeric biphenyl monophosphine ligands with tunable dihedral angles was accordingly synthesized successfully without a resolution step being needed. Using these ligands, different kinds of axially chiral 1,1′‐biaryl‐2‐phosphonates including the first reported quinolyl biaryl phosphonates were prepared in 42–97% yields with up to 96% ee via palladium‐catalyzed asymmetric Suzuki coupling reactions.