We have discovered that different aziridines and azetidines undergo efficient ring-opening reactions in liquid SO2 with metal halides and thiols as nuchleophile sources. A novel method for the synthesis of sulfones also has been elaborated. Major step for further sulfone generation is bora-ene reaction of sulfur dioxide and substituted potassium trifluoroborate giving mixed sulfinic/boric anhydrides (transformation B). We investigated glycosylation reaction with a wide range of O-, and Snucleophiles of different monosaccharides in liquid SO2 (transformation C). We have also found that liquid SO2 facilitates Meyer–Schuster and Rupe rearrangement reactions (transformation D).