Palladium-catalyzed regio- and stereoselective formate reduction of fluorine-containing allylic mesylates. A new entry for the construction of a tertiary carbon attached with a fluoroalkyl group.

The regioselective palladium-catalyzed formate reduction of gamma-fluoroalkylated allylic esters is described. Reduction of the allylic esters under the influence of palladium with a monodentate phosphine ligand proceeded preferentially at the gamma position, the corresponding reduction products with a fluoroalkyl group at the tertiary carbon being afforded in high yields. When the chiral allylic ester was employed, complete chirality transfer was observed, leading to the optically active materials in high yields.

Highly regio- and stereoselective carbostannylation reaction of fluorine-containing internal acetylenes with allylstannanes.

Carbostannylation of fluoroalkylated alkynes with various allylstannanes in the presence of AIBN was investigated. In the case of the allylstannane having an electron-withdrawing group at the beta position, the reaction proceeded highly regio- and stereoselectively to give the corresponding allylstannylated products in high yields. Even in the absence of AIBN, the reaction took place smoothly in a highly regio- and stereoselective manner under an atmosphere of air. Thus-obtained vinylstannanes were subjected to the Migita-Kosugi-Stille coupling reaction conditions, affording the tetrasubstituted alkenes in excellent yields.

The fluorine-containing pi-allylmetal complex. The transition metal-catalyzed allylic substitution reaction of fluorinated allyl mesylates with various carbon nucleophiles.

The allylic substitution reaction of [small alpha]-fluoroalkylated allyl mesylates with various carbon nucleophiles in the presence of transition metal catalyst (Pd and Mo) proceeded with high regioselectivity to give the corresponding [gamma]-fluoroalkylated products in excellent yields.