Dynamic Kinetic Cross-Coupling Strategy for the Asymmetric Synthesis of Axially Chiral Heterobiaryls

by Abel Ros, Beatriz Estepa, Pedro Ramírez-López, Eleuterio Álvarez, Rosario Fernández and José M. Lassaletta

A dynamic kinetic asymmetric transformation (DYKAT) technique has been designed for the synthesis of 2′-substituted 2-aryl pyridines/isoquinolines and related heterobiaryls. In this way, the Pd(0)-catalyzed coupling of racemic 2-triflates with aryl boroxines using a TADDOL-derived phosphoramidite as the ligand provides the corresponding coupling products with good to excellent enantioselectivities. Structural studies support that the formation of configurationally labile oxidative addition palladacycles is the key for the success of the methodology.

Journal of the American Chemical Society

DOI:10.1021/ja4087819