A new synthetic route to 2-sulfonylbenzothiazoles (BtsR) employing cascade SO2--NCS nucleophilic addition and CuI-catalysed S-C(sp2) coupling was developed. Structurally diverse BtsR molecules were readily afforded in high yields from the rapid and benign reaction of 2-iodoarylisothiocyanates with sodium sulfinates in DMSO, generally without the need for further column isolation.