Palladium-Catalyzed Asymmetric Construction of Vicinal Tertiary and All-Carbon Quaternary Stereocenters by Allylation of β-Ketocarbonyls with Morita-Baylis-Hillman Adducts.

Palladium-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of β-ketocarbonyls with Morita-Baylis-Hillman adducts has been developed using a spiroketal-based diphosphine (SKP) as the ligand, thus affording a range of densely functionalized products bearing vicinal tertiary and all-carbon quaternary stereodyad in high selectivities. The utility of the protocol was demonstrated by the facile synthesis of some complex molecules by simple product transformations.