Thiolene dioxides

When 3-thiolene dioxide is treated with hydrogen peroxide, the corresponding epoxide is obtained313. The 3,4-trans-diols can be obtained by hydrolysis under acidic conditions (equation 120). 

Thio-Claisen rearrangement 746-748 Thioketene 5-oxides photolysis of 878 reactions of 277 Thiolane dioxides formula of 382 NMR spectra of 460 reactions of 604 synthesis of 461 Thiolane oxides 747 formula of 382 IR spectra of 461 synthesis of 461, 462, 752 Thiolanes, photolysis of 881 Thiolene dioxides formula of 382 NMR spectra of 460 reactions of 464, 465 synthesis of 461 Thiolene oxides formula of 382 synthesis of 461, 746 Thiols... 

Five membered ring sulfones (thiolene-1, 1-dioxides, sulfolenes or dihydrothiophene-1, 1-dioxides) can be obtained by peracid oxidation of tetrahydrothiophene. The extrusion of sulfure dioxide from dihydrothiophene-1,1 dioxides or sulfolenes like (178) has been much studied as it provides a synthetic route to dienes, e.g. butadiene (152) (Scheme 70). The reverse reaction provides a method of synthesis of sulfolene (178) from butadiene (152) and sulfur dioxide. Thiolene dioxides or sulfolenes can be generally prepared by addition of sulfur dioxide to conjugated dienes for example, 1,4-dimethylbutadiene (179) in the presence of sulfure dioxide, triethylamine and formic acid affords 2,5-dimethylsulfolene (180) (Scheme 71). 

Catalytic hydrogenation of thiolene 1,1-dioxides to thiolane 1,1-dioxides 97UK463. 

Two attractive routes to thiolene oxide and dioxide are the diene-SO104 and diene-S02298 cycloadditions, respectively. These cycloadditions are highly stereoselective at both carbons of the diene systems and at sulfur (see equation 62 for specifics) which, in the case of sulfoxide formation, proceed via attack of triplet SO on the diene. Equation 112 shows an example of such a cycloaddition104. The overall yields are significantly improved by running the cycloadditions in the absence of oxygen and by the use of excess diene. 

Since sulfoxides and sulfones are versatile synthetic intermediates, and since in both the thiolene oxide and dioxides the reverse dethionylation114 ( — SO), and cheletropic extrusion of sulfur dioxide296, respectively, readily take place thermally, these cycloadditions are expected to find a useful place in organic synthesis. It should be kept in mind, however, that the retrograde SO-diene reaction and interconversion of the thiolene oxides compete effectively against SO extrusion on heating, and that diene isomerization accompanies the forward reaction (SO + diene). 

Treatment of the substituted aminosulfolene (253) with phenyl isothiocyanate in refluxing benzene-pyridine (2 1) gave the perhydrothieno[3,4-rf]imidazole-2-thione 5,5-dioxide (254) (82CHE328). Reaction of 4-halo-2-thiolene (or -thiolane) 1,1-dioxides with dithiocarbamates proceeded similarly to give perhydrothieno[3,4-[Pg.1011]

Thiolene 1,1-dioxides and thiolane 1,1-dioxides in synthesis of biologically active compounds 85MI9. 

There are relatively few reports involving the Michael addition of cyanomethylphosphonate anions to unsaturated compounds. The reaction provides a methodology for the elaboration of new reagents but more frequently is used for the preparation of phosphonylated heterocycles. Under basic conditions, diethyl cyanomethylphosphonate adds to benzalacetophenone and 2-bcnzylidcne-3-methyl-4-nitro-3-thiolene-l,l-dioxide to give the addition products in modest yields.- - - " ... 

Nikolaenko, T.Y., Trukhin, E.V., Tebbi, J., and Berestovitskaya, V.M., Reaction of phosphorylated CH acids with 2-bcnz.ylidcne-3-inethyl-4-nilro-3-thiolene 1,1-dioxide, Zh. Obshch. Khim., 66, 1043, 1996 Russ. J. Gen. Chem. (Engl. Transl.), 66, 1018, 1996. 

Cycloadditions involving unsaturated five- and six-membered rings containing sulphur have offered convenient routes to thiolan and thian derivatives. 3-Thiabicyclo[3,l,0]hexane 3,3-dioxide (27a) and its 2-methyl-and cij -2,4-dimethyl-derivatives (27b) and (27c) have been synthesized from the appropriate thiolen 1,1-dioxides by cycloaddition of diazomethane... 

Substituent effects in diorganyl sulfones, 3- and trans-3,4-substituted thiolane 1,1-dioxides and 4-substituted 2-thiolene 1,1-dioxides have been investigated and correlations with and in analogous compounds as well as with Taft (Hammett) electronic parameters have been reported. Stereochemical effects on S shielding have been studied such as the stereomeric sulfones [4] and [5]. 

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