Palladium-Catalyzed α-Allylation of Secondary Nitroalkanes with Allylic Alcohols and Strategic Exploitation of Seebach's Reagent for the Total Synthesis of (±)-Adalinine

A method is reported for the catalytic direct coupling of allylic alcohols and nitroalkanes. In the allylation process, the synergistic action of palladium complexes and titanium(IV) alkoxide facilitates the formation of nitronate and π-allylpalladium intermediate. In the cases of reluctant allylations, typically with sterically demanding nitroalkanes, we found the addition of substoichiometric amount of DBU greatly facilitates the desired transformation. We also accomplished a total synthesis of (±)-adalinine through a homoallyl nitroalkane derived from Seebach's reagent.