π-Allylmetal complexes derived from α-fluoroalkylated allyl mesylates
react smoothly with various nucleophiles such as stabilized carbanions,
carboxylates, and amines at the carbon distal to a fluoroalkyl group in a highly
regioselective manner to give the corresponding γ-products in high to excellent
yields. Treatment of the above fluorine-containing π-allylmetal complexes with
hydride nucleophile gives the adducts derived from the hydride attacking on the
carbon attached to a fluoroalkyl group. The γ-adducts, obtained by the reaction of
π-allylpalladium complex with α-methoxy acetate or N-protected glycine, undergo
smooth Ireland-Claisen rearrangement to give the corresponding multifunctionalized
molecules in high yields. On the other hand, the reaction of α-
fluoroalkylated propargylic mesylates with zinc reagents or stabilized carbanions
in the presence of palladium catalyst affords fluorine-containing allene or furan
derivatives respectively, in high yields, via allenylpalladium complex.
