The direct reaction of two equivalents of lithium diisopropylamide (LDA) with 2-bromo-3,3,3-trifluoropropene gave lithium trifluoromethylacetylide, which was then trapped with aromatic aldehydes to produce trifluoromethyl propargyl alcohols(2) in high yields. Treatment of 2 with LiAlH~4 and followed by I~2 provided (Z)- 3-iodo-3-trifluoromethyl-1-aryl allylic alcohols(1). In the presence of 1 equivalent of triethylamine, Pd(PPh~3)~4/CuI catalyzed cross- coupling of 1 with terminal alkynes in THF at 50℃ afforded conjugated (E)-3-alkynyl-3-trifluoromethyl allylic alcohols 5. When triethylamine was used as both base and solvent, the Pd(PPh~3)~4/CuI catalyzed crosscoupling of 1 with terminal alkynes led to ketones 4 instead of the expected 5. Mechanistic studies revealed that 5 was easily rearranged to 4 in the presence of triethylamine.

Key words: PALLADIUM, TRIPHENYLPHOSPHINE, CUPROUS IODIDE, CATALYST, REARRANGEMENT REACTION, TRIFLUOMETHYL, COUPLED, CROSSED IMMUNITY, PALLADIUM COMPOUNDS