Collect. Czech. Chem. Commun. 2002, 67, 1421-1435

Fluorine-Containing Allenylpalladium Complexes. Synthesis of Optically Active Fluoroalkylated Allenes and Furan Derivatives

Tsutomu Konno*, Mitsuru Tanikawa, Takashi Ishihara and Hiroki Yamanaka

Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Sakyo-ku, Matsugasaki, Kyoto 606-8585, Japan


The reaction of fluoroalkylated propargyl mesylates with various nucleophiles, such as zinc reagents and enolates derived from 1,3-dicarbonyl compounds, in the presence of a palladium catalyst was investigated in detail. Various zinc reagents participated in the coupling reaction to give the corresponding fluoroalkylated allenes in good yields. When chiral mesylates were employed, the corresponding optically active allenes were obtained without any loss of enantiomeric purity in the reaction. On the other hand, treatment of trifluoromethylated propargyl mesylate with stabilized carbanions derived from methyl acetoacetate, acetylacetone, and diethyl malonate afforded fluorine-containing furan derivatives in moderate to high yields.

Keywords: Fluorine-containing allenylpalladium complexes; Allenes; Alkynes; Propargyl esters; Furanes; Fluorinated compounds; Palladium catalysis; Enantioselective synthesis; Cross-coupling reactions.

References: 42 live references.