Desulfurization of Dithiirane S-Oxides Oxidative Rearrangement of Aryl Benzyl Sulfides Oxidative Ring Opening of Thiophenes 27.4.1.1.10 Method 10: Desulfurization of Dithiirane S-Oxides

The manuscript is an update to the earlier Science of Synthesis contribution describing methods for the synthesis and new applications of thiocarbonyl S-oxides (sulfines) and thiocarbonyl S-imides. In general, thiocarbonyl S-oxides are more stable and in many instances they can be isolated in substance. The in situ generated thiocarbonyl S-imides are efficient ‘sulfur transferring agents’ via the isomeric thiaziridines formed as products of electrocyclic ring closure. Stable thiocarbonyl S-imides, derived form hexafluorothioacetone, are useful 1,3-dipoles applied for the preparation of fluorinated, five-membered heterocycles. Posted at the Zurich Open Repository and Archive, University of Zurich ZORA URL: https://doi.org/10.5167/uzh-96486 Submitted Version Originally published at: Mloston, Grzegorz; Heimgartner, Heinz (2014). Thioaldehyde and Thioketone S-Oxides and S-Imides (Sulfines and Derivatives) (Update 2014). In: Bronsted Nielsen, M; Krause, N; Marek, I; Schaumann, E; Wirth, T. Science of Synthesis Knowledge Updates: 2014/2. Stuttgart: Thieme Verlag, 393-401. 27.4 Product Class 4: Thioaldehyde and Thioketone S-Oxides and SImides (Sulfines and Derivatives) Mlostoń, G., Heimgartner, H., in Science of Synthesis, 27 (update 2013) General Introduction Thioaldehyde and thioketone S-oxides (sulfines) as well as structurally similar S-imides are considered as so called S-centered heterocumulenes. Numerous representatives are isolated in substances, however, in some instances they are also postulated as reactive intermediates. In the last decade, no reports on new methods for the generation of thiocarbonyl S-oxides or thiocarbonyl S-imides were published in generally available literature. However, some earlier reported approaches should be added to the list of methods presented in the first edition. 27.4.1 Product Subclass 1: Thioketone S-Oxides (Sulfines) Mlostoń, G.; Heimgartner, H.; in Scienceof Synthesis, 27 (update 2013) General Introduction: In a recent review, the chemistry of sulfines is summarized. In addition to the earlier presented procedures, there are three other methods known, which deserve mentioning. None of these methods is based on a reaction with thioketones. Gas-phase thermolysis of 1,3-dithietane S,S’-dioxide is an excellent procedure for the generation of thioformaldehyde S-oxide for physicochemical studies in matrices. See: