Nickel-Catalyzed Atroposelective Cross-Electrophile Coupling of Aryl Halides: A General and Practical Route to Diverse MOP-type Ligands

We report a highly cross- and atroposelective coupling between ortho-(chloro)arylphosphine oxides and ortho-(bromo)arylethers. This previously unknown asymmetric nickel-catalyzed reaction offers a direct route to highly enantioenriched axially chiral biaryl monophos-phine oxides that are difficult to access by other means. These products can be readily reduced to generate chiral MOP-type ligands bear-ing complex skeletal backbones. The utility of these chiral ligands in asymmetric catalysis is also demonstrated.