P‐Stereogenic Chiral Phosphine−Palladium Complex Catalyzed Enantioselective Synthesis of Phosphoryl‐Substituted Atropisomeric Vinylarenes

P‐Stereogenic chiral phosphine BI‐BOP is employed for the first time as ligand to promote catalytic enantioselective synthesis of phosphoryl‐substituted atropisomeric vinylarenes through a palladium−carbene pathway. This strategy utilizes 10 mol% palladium(II) acetate, 10 mol% phosphine ligand as well as a variety of N‐tosylhydrazones and phosphoryl‐substituted aryl bromides as the reaction partners. The desired axially chiral vinylarenes were isolated with up to 80% yield and 96:4 er, and can be further converted effectively and stereoselectively into dialkylphosphoryl‐substituted atropisomeric arenes through a Grignard reaction. This protocol offers a general approach to synthesize phosphoryl‐substituted atropisomeric vinylarenes with high enantiomeric purities.