Palladium-acetate catalyst for regioselective direct arylation at C2 of 3-furanyl or 3-thiophenyl acrylates with inhibition of Heck type reaction

Lu Chen (1) , Christian Bruneau (1) , Pierre H. Dixneuf (1) , Henri Doucet (1)

1 ISCR - Institut des Sciences Chimiques de Rennes

Pd(OAc)2/KOAc was found to be an efficient catalytic system for the direct arylation of thiophene and furan derivatives bearing an acrylate at C3. The selectivity of the reaction strongly depends on the nature of the coordinating base. Na2CO3 and Li2CO3 favours the Heck type reaction; whereas the use of KOAc or CsOAc promotes regioselective arylation at C2 of the heteroarene and inhibits the Heck type reaction. The direct arylation products were obtained in moderate to good yields using only 0.1 mol % of catalyst. Electron-withdrawing substituent on aryl bromide, such as acetyl, formyl, ester, nitrile or nitro, favours the reaction; whereas electron-donating ones are unfavourable.

Mots clés: Palladium; Catalysis; Heteroarenes; Aryl bromides; C-H functionalisation

Domaines: Catalyse

Lu Chen, Christian Bruneau, Pierre H. Dixneuf, Henri Doucet. Palladium-acetate catalyst for regioselective direct arylation at C2 of 3-furanyl or 3-thiophenyl acrylates with inhibition of Heck type reaction. Tetrahedron, 2013, 69 (22), pp.4381-4388. ⟨10.1016/j.tet.2012.12.061⟩. ⟨hal-00879862⟩