A selection of metal-catalyzed C− C bond-forming strategies has been evaluated in the synthesis of a series of meta-substituted thienylbenzenes,(T n) 2C6H4 and (T n) 3C6H3 (n= 1, 2; T1= 2-thienyl; T2= 2, 2′-bithien-5-yl). Kumada coupling reactions catalyzed by PdCl2 (dppf) between the appropriate thienyl Grignard and either 1, 3-or 1, 3, 5-bromo-or iodobenzenes were found to be the most reliable in terms of convenience, selectivity and ...