The present review is devoted to summarizing the recent advances (2015–2017) in the field of metal-catalysed group-directed C–H functionalisation.

The direct arylation of benzo[b]furan, benzo[b]thiophene, and indole has been studied by using aromatic bromides as the aryl source. The protocol employing common reagents and a Pd catalyst has led to the regioselective arylation of these heterocycles at the 2-position. A range of functional groups were tolerated, providing quick access to a variety of arylated benzo-fused heterocycles that would be accessible more elaborately using classical synthetic strategies. This is the first systematic study of the direct arylation of benzo[b]furan.

An improved protocol for the direct arylation of N-phenyl-N-benzyl(thiazol-2-yl)amine by using aryl bromides as aryl donors is reported. The procedure was compared with a previously reported protocol in which aryl iodides were used as arylating agents. The improved direct arylation protocol was applied to structurally isomeric and nonaromatic 3-benzyl-N-phenylthiazol-2(3H)-imine. The two substrates for direct [a]

Direct Arylation of Benzo[b]furan and Other Benzo-Fused Heterocycles. -The novel protocol allows the regioselective direct arylation of benzo-fused heterocycles with arylbromides to produce the corresponding 2-substituted products in moderate yields. 3-Arylated and bis-arylated by-products are observed in several cases in low quantities. Furthermore, benzofurans (III) undergo direct arylation on C-3 providing bis-arylated products. -(DAO-HUY, T.; HAIDER, M.; GLATZ, F.; SCHNUERCH*, M.; MIHOVILOVIC, M. D.; Eur. J. Org. Chem. 2014, 36, 8119-8125, http://dx.doi.org/10.1002/ejoc.201403125 ; Inst. Appl. Synth. Chem., Wien Univ. Technol., A-1060 Wien, Austria; Eng.) -Mais 20-117

A series of 2-arylbenzofurans and 2-arylbenzothiophenes was synthesized carrying three different side chains in position five. The synthesized compounds were tested for NF-κB inhibition to establish a structure activity relationship. It was found that both, the side chain in position five and the substitution pattern of the aryl moiety in position two have a significant influence on the inhibitory activity.