9-Substituted 2-chloro-6-sulfonylpurines provide 6-azido-2-sulfonylpurine derivatives with 61-83% yields when treated with sodium azide. Under optimized reaction conditions, the title compounds are obtained in a one-pot process, which involves a sequential treatment of 2,6-dichloropurines with a selected sodium sulfinate and sodium azide. Such a sulfonyl group dance (functional group swap) results from a cascade of SNAr reactions, which are facilitated by azidoazomethine-tetrazole (azide-tetrazole) tautomeric equilibrium. The formation of Meisenheimer-type intermediates as tetrazolopurine tautomers was supported by various spectroscopic methods, including 15N NMR.