Collect. Czech. Chem. Commun. 1999, 64, 649-672

Coupling Reactions of ortho-Substituted Halobenzenes with Alkynes. The Synthesis of Phenylacetylenes and Symmetrical or Unsymmetrical 1,2-Diphenylacetylenes

Irena G. Stará*, Ivo Starý*, Adrian Kollárovič, Filip Teplý, David Šaman and Pavel Fiedler

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo n. 2, 166 10 Prague 6, Czech Republic


The Pd- or Pd/Cu-catalyzed coupling reactions of halobenzenes bearing the methyl, hydroxymethyl, acetoxymethyl, methoxycarbonyl, or both methoxy and 4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl groups in the ortho-position with gaseous or metallated acetylene, (trialkylsilyl)acetylenes, and arylacetylenes have been systematically studied. Various functionalized aryl- or diarylacetylenes have been synthesized in good to excellent yields. Whereas additional fluoro, nitro, or methoxy group attached to the benzene ring does not interfere in the coupling reactions, the presence of a methoxycarbonyl requires a careful optimization of reaction conditions to achieve moderate yields.

Keywords: Halobenzenes; Phenylacetylenes; Diphenylacetylenes; Cross-coupling reactions; Palladium catalysis; Arenes; Alkynes.