On the Synthesis of Sulfoxonium Ylides: New Aspects of the Chemistry of 1,3-Dithietane 1,1,3,3-Tetraoxide and 1,3,5-Trithiane 1,1,3,3,5,5-Hexaoxide

Sulfoxonium ylides 3a‐h were synthesized by silylation of the cyclic methylene disulfones 1,3‐dithietane 1,1,3,3‐tetraoxide (1) and 1,3,5‐trithiane 1,1,3,3,5,5‐hexaoxide (4) with the silylating agents silyl nonafluorobutanesulfonates. The structure and constitution of the ylides were established with 1H‐NMR, 13C‐NMR, 29Si‐NMR spectroscopy, mass spectrometry, and elemental analysis. On the route to the sulfoxonium ylides a new class of unsaturated disulfenes 7, 8, 12, 13 of 1 and 4 were synthesized via Knoevenagel and substitution reactions. Dianions of newly formed alkyl disulfenes 16a, b, e, f, and the trianion 17 were prepared and characterized by 1H‐NMR and 13C‐NMR spectroscopy and compared with the results of the ylides.