Multi-substituted benzo[b]thiophenes are of considerable importance, as they exhibit various biological activities 1 and also provide useful properties in materials science. 2 A number of methods to synthesise this class of compounds have been reported in recent years, 3 most of which involve the cyclisation of benzenethiol derivatives. However, facile and versatile methods to access multi-substituted benzo[b]thiophenes are still limited. Furthermore, catalytic cyclisation ...