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. [ABSTRACT FROM AUTHOR]