A catalytic method for the site-selective and enantioselective synthesis of functionalized arenes by the intermolecular hydroarylation of terminal and internal 1,3dienes 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. Scheme 1. Catalytic enantioselective hydroarylations of 1,3-dienes.

A catalytic method for the site-selective and enantioselective synthesis of functionalized arenes by the intermolecular hydroarylation of terminal and internal 1,3dienes 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. Scheme 1. Catalytic enantioselective hydroarylations of 1,3-dienes.