Abstract

AbstractP‐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.magnified image

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