C-Aryl Glycosylation: Palladium-Catalyzed Aryl-Allyl Coupling of Achmatowicz Rearrangement Products with Arylboronic Acids.

The first Pd-catalyzed arylation of Achmatowicz rearrangement products with arylboronic acids under mild conditions (rt) to provide the synthetically versatile C-aryl dihydropyranones is reported. It is found that the 4-keto group of Achmatowicz products is essential to increase the reactivity of the Pd-π-allyl complex toward arylboronic acids and that phosphine as the palladium ligand would be destructive to the reaction. This new coupling method addresses the major limitations of previous Pd-catalyzed allyl-aryl couplings of 2,3-unsaturated glycosides with an aryl Grignard or aryl zinc reagent.