Synthesis of chiral-bridged atropisomeric monophosphine ligands with tunable dihedral angles and their applications in asymmetric Suzuki-Miyaura coupling reactions

摘要

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.