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

Abstract

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%).