Enantioselective Synthesis of Functionalized Arenes by Nickel‐Catalyzed Site‐Selective Hydroarylation of 1,3‐Dienes with Aryl Boronates

A catalytic method for the site‐selective and enantioselective synthesis of functionalized arenes by the intermolecular hydroarylation of terminal and internal 1,3‐dienes with aryl pinacolato boronates is reported. The reactions are promoted by 5.0 mol % of a readily available monodentate phosphoramidite‐Ni complex in ethanol, affording a variety of enantioenriched products in up to 96 % yield and 99:1 er. Mechanistic studies indicate that Ni–allyl formation is irreversible and related to the nature of the arylboronate. A catalytic method for the site‐ and enantioselective synthesis of functionalized arenes through intermolecular hydroarylation of 1,3‐dienes with aryl pinacolato boronates is reported. The reactions are promoted by 5.0 mol % of a phosphoramidite–Ni complex in ethanol, affording enantioenriched products in up to >95:5 rr and 99:1 er. Mechanistic studies indicate that Ni–allyl formation is irreversible and related to the nature of the arylboronate.