It is important to note that this method worked efficiently well on milligram, gram, and even multigram scales (2, 13) without any significant change in the reaction yield. Most products were crystalline solids, and could be purified easily by crystallization. For liquid/oil compounds the purification was performed by column chromatography. The molecular structures of products 8, 9, 12 and 29 were confirmed by X-ray crystallographic analysis. Next, we tried various N,C-bis-nucleophiles (Scheme 3). The reaction of vinamidinium salt 1 with glycine derivates gave pyrroles 31-33 in 49-95% yield. Analogously, pyridones 34-36 and pyridines 37, 38 were synthesized in 46-92% yield. The reaction of salt 1 with various amino pyrazoles, amino isoxazoles, amino thiazoles, amino pyrroles, and amino thiophenes gave the corresponding bicyclic heterocycles 39-46 in 76-93% yield. It is worth noting that while the reaction of reagent 1 with methyl 5-amino-2-furoate in pyridine gave the desired bicyclic product 47, the analogous reaction in acetonitrile led to the selective formation of the non-cyclized compound 48. The reaction of 1 with electron-rich aminouracil, aminopyridine, and anilines gave bicyclic products 49-54 in 49-89% yield. The structure of compounds 34, 41, 42 and 45 was confirmed by Xray crystallographic analysis. Remarkably, despite the simplicity of the current approach to methyl sulfones, the preparation of all compounds 8-54 has never been described before by any methods.