Palladium‐Catalyzed Asymmetric Allylic Allylation of Racemic Morita–Baylis–Hillman Adducts

A palladium‐catalyzed asymmetric allyl–allyl cross‐coupling of acetates of racemic Morita–Baylis–Hillman adducts and allylB(pin) has been developed using a spiroketal‐based bis(phosphine) as the chiral ligand, thus affording a series of chiral 1,5‐dienes bearing a vinylic ester functionality in good yields, high branched regioselectivities, and uniformly excellent enantioselectivities (95–99 % ee). Further synthetic manipulations of the allylation products provided novel ways for rapid access to a range of chiral polycyclic lactones and polycyclic lactams, as well as the antidepressant drug (−)‐Paroxetine, in high optical purities.