Palladium-catalyzed direct 5-arylation of formyl- or acetyl-halothiophene derivatives

Pd(OAc)2 was found to catalyze the direct arylation of some functionalized halothiophene derivatives allowing the synthesis in only one step of polyfunctionalized arylated thiophenes. In the presence of 2-acetyl-3-chlorothiophene, 2-acetyl-4-chlorothiophene, 2-acetyl-3-bromothiophene diethylacetal or 2-(4-bromothiophen-2-yl)-[1,3]dioxolane, and a variety of aryl bromides, the 5-arylation products were obtained in moderate to high yields employing only 0.5 mol% catalyst. On the other hand, the use of 2-formyl-3-chlorothiophene, 2-acetyl-3-bromothiophene or 2-formyl-3-bromothiophene gave disappointing results.

Pd(OAc)2 catalyzes the direct arylation of some formyl- or acetyl-halothiophenes. With several substrates, the integrity of the carbon–halide bond was maintained.Figure optionsDownload as PowerPoint slideHighlights
► Catalyzed direct arylations of formyl- or acetyl-halothiophene derivatives.
► The integrity of the carbon–halide bond was maintained.
► A low loading of palladium catalyst was employed.
► Atom-economic access to arylated thiophenes.