Pd-Catalyzed Regioselective and Stereospecific Suzuki-Miyaura Coupling of Allylic Carbonates with Arylboronic Acids

The Pd-catalyzed Suzuki-Miyaura coupling reaction of unsymmetric 1,3-disubstituted secondary allylic carbonates with arylboronic acids has been developed in a wet solvent under a base-free system to afford allyl-aryl coupling products in a high level of isolated yields with complete regio- and E/Z-selectivities with good to excellent chemoselectivities. The coupling reaction of optically active allyl carbonates gave allyl-aryl coupling products with excellent enantioselectivities with inversion of the stereochemistry. This coupling method was successfully applied to the synthesis of (S)-naproxen.