Catalytic Asymmetric Synthesis of Branched Chiral Allylic Phenyl Ethers from ( E )‐Allylic Alcohols

The first di‐μ‐amidate dipalladium complexes and a new di‐μ‐carboxylate dipalladium complex of the COP (cobalt oxazoline palladacycle) palladium(II) catalyst family are reported and characterized crystallographically. The di‐μ‐amidate complex 3 and its enantiomer ( ent ‐ 3 ) are the first asymmetric catalysts that allow commercially available, or readily accessible, ( E )‐2‐alken‐1‐ols to be transformed to enantioenriched branched allylic aryl ethers upon reaction of their trichloroacetimidate derivatives with phenols. The 3‐aryloxy‐1‐alkene products are formed in high enantiomeric purity (typically 90–98% ee ) and useful yields (61–88%).