Thiirane 5,5-dioxides, elimination

The higher strain energy in thiirene dioxides (19) compared to thiirane dioxides (17) is obvious. Yet, the elimination of sulfur dioxide from the latter is significantly faster than one would expect for a thermally allowed concerted process. Consequently, either aromatic-type conjugative stabilization effects are operative in thiirene dioxides2,12 or the relative ease of S02 elimination reflects the relative thermodynamic stability of the (diradical )99 intermediates involved in the nonconcerted stepwise elimination process. 

The elimination of sulfur dioxide from thiirane dioxides leading to the corresponding alkenes is not the only result of base-induced reactions other products are also formed. This fact raises the question of the mechanistic pathway of this reaction. In general, the thiirane dioxide is treated with a large excess of the base in an appropriate solvent for several hours at room temperature or below. Bases commonly used are 2n NaOH (in water), NaOCH3 (in methanol), t-BuO-K + (in f-BuOH) and BuLi (in tetrahydrofuran) or KOH-CCU (in t-BuOH)16-19"112 113. 

There is no clear reason to prefer either of these mechanisms, since stereochemical and kinetic data are lacking. Solvent effects also give no suggestion about the problem. It is possible that the carbon-carbon bond is weakened by an increasing number of phenyl substituents, resulting in more carbon-carbon bond cleavage products, as is indeed found experimentally. All these reductive reactions of thiirane dioxides with metal hydrides are accompanied by the formation of the corresponding alkenes via the usual elimination of sulfur dioxide. 

The Ramberg-Backlund Reaction. a-Halosulfones undergo a related rearrangement known as the Ramberg-Backlund reaction.91 The carbanion formed by deprotonation gives an unstable thiirane dioxide that decomposes with elimination of sulfur dioxide. This elimination step is considered to be a concerted cycloelimination. 

The thiirane dioxides decompose with elimination of sulfur dioxide. The reaction is useful for the synthesis of certain types of olefins. 

The Ramberg-Backlund reaction converts a-halo sulfones into alkenes in the presence of a base with extrusion of S02. The a-metallated intermediates formed by the action of a polar base undergo 1,3-elimination with formation of unstable thiirane dioxides of type 83 that decompose into alkenes - - SO2 (cheletropic elimination). Halogenation is done under basic conditions using CBr2F2. The reactions has been applied to the synthesis of C-glycosides of type 84, as illustrated in Scheme 22.23. " ... 

The symmetric diarylthiirene oxides (18) are much more thermally stable than the corresponding saturated thiiranes and unsaturated thiirene dioxides. Thus, the thiirene oxide 18a shows only slight decomposition after 24 hours of reflux in benzene, whereas the analogous sulfone 19b fragments completely to SO2 and diphenylacetylene after less than six hours under the same conditions Irradiation of the oxide 18a, however, does result in the elimination of sulfur monoxide and formation of diphenylacetylene. Its thermolysis at 130 °C afforded benzil as the only isolable product, implying that SO is not being eliminated in this thermolytic process. 

Extrusion (or elimination) of sulfur from thiiranes and thiirenes is a facile process. Virtually all thiiranes and thiirenes, as well as their oxides and dioxides, undergo thermal extrusion of the sulfur moiety with increasing facility according to the trend S < < SO < S02. The thermolytic desulfurization mechanism is more complex than a simple cheletropic extrusion (85TL2789). 

The use of optically active enamines in [2 + 2] cycloadditions with thiocarbonyl 5.5-dioxides gives asymmetric induction in the product thiirane 1,1-dioxides. Thus, when thioformaldehyde S,S-dioxide, generated from methanesulfonyl chloride and triethylamine, is treated with optically active AM-phenylethyl-Af-methylpropanal enamine, a mixture of diastereomeric thietane 1.1-dioxides 6 is formed quantitatively. Removal of the chiral 1-phenylethyl auxiliary followed by Hoffmann elimination gives (-+ )-(5)-2-methyl-2//-thiete 1,1-dioxide (7) with 6% ee1,8. 

The three-, four-and five-membered cyclic sulfones have some interesting reactions. Three-membered ring sulfones, called thiirane-1,1-dioxides or episulfones, can be prepared by reaction of a diazoalkane, e.g. (160), with sulfur dioxide (Scheme 63). The reaction affords a mixture of the cis-episulfone (161) and trans-episulfone (162), and both isomers can be isolated by fractional crystallisation at low temperature. Another method of preparation of episulfones is by treatment of a diazoalkane with a sulfonyl chloride (containing a-hydrogen atoms) and a tertiary amine (Scheme 64). Both these syntheses involve the formation of the highly reactive sulfene intermediate (163) (see Chapter 7, p. 114) episulfones on warming eliminate sulfur dioxide to form the alkene (164) as indicated in Scheme 64.7... 

Carbon-carbon bcmd cleavage of the strained thiiran 1,1-dioxide intermediate (116) followed by rearrangement to (117) is suggested to explain the course of the base-induced elimination of hydrogen chloride from (115). ... 

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