Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

The first nickel-catalyzed highly enantioselective reductive Ullmann coupling of ortho-chlorinated aryl aldehyde was achieved under mild reaction conditions with a chiral 2,2'-bipyridine ligand (+)-DTB-SBpy, thus providing axially chiral biphenyl or binaphthyl dials with up to 99 % yield and 99.5:0.5 er. The versatility of the products as common synthetic intermediates for diverse axially chiral ligands, catalysts, and functional molecules was demonstrated by short-step transformations. This protocol also allowed the concise and highly enantioselective formal total synthesis of biologically active natural products (+)-kotanin, (-)-isoschizandrin and (+)-gossypol.