An efficient bromocyclization process of ortho-substituted arylmethyl sulfide promoted by N-methyl-pyrrolidin-2-one hydrotribromide led to the synthesis of 3-bromo-2-(2-(di)chlorovinyl)benzothiophene as a polyhalogenated platform. Various arylations on the C3 atom of such di-substituted benzothiophenes and further functionalizations at the chlorine atoms of the benzothiophenes afforded efficient and rapid access to a small library of stereo-defined 2,3-disubstituted benzothiophenes.