From sulfoxides

Selective or preferential extraction of diastereomeric salts formed from sulfoxide carboxylic acids and alkaloids in water relative to the reciprocal diastereomeric salts has been studied33. 

Corey and Chaykovsky had discovered that dimethyl sulfoxide is converted to methyl-sulfinyl carbanion upon treatment with sodium hydride114 and that this conjugate base of DMSO reacts with various electrophiles115. This finding has opened up various reactions with a-sulfmyl carbanions derived from sulfoxides, since the sulfinyl function can be removed either by thermolysis or by subjecting the compound to reductive desulfurization. Thus a-sulfmyl carbanions have become versatile synthetically useful reagents. 

This review is concerned with the formation of cation radicals and anion radicals from sulfoxides and sulfones. First the clear-cut evidence for this formation is summarized (ESR spectroscopy, pulse radiolysis in particular) followed by a discussion of the mechanisms of reactions with chemical oxidants and reductants in which such intermediates are proposed. In this section, the reactions of a-sulfonyl and oc-sulfinyl carbanions in which the electron transfer process has been proposed are also dealt with. The last section describes photochemical reactions involving anion and cation radicals of sulfoxides and sulfones. The electrochemistry of this class of compounds is covered in the chapter written by Simonet1 and is not discussed here some electrochemical data will however be used during the discussion of mechanisms (some reduction potential values are given in Table 1). 

Cation and anion radicals form from sulfoxides or sulfones by either chemical or electrochemical oxidation and reduction, respectively. The ability of compounds to accept... 

TABLE 6. ESR parameters for radical cations arising from sulfoxides or sulfones... 

Sulfoxide reductase Removal of oxygen from sulfoxide Sulfinpyrazone... 

C. Oxygen Atom Transfer from Sulfoxide to Sulfide... 

Allenes as versatile synthons including Diels-Alder reactions and especially intramolecular cycloadditions of this type were reviewed by Aso and Kanematsu [338], In some cases of intramolecular Diels-Alder reactions of open-chain starting materials such as 340 [339], 342 [339] and similar acceptor-substituted allenes [156], the formation of two new six-membered rings seems to be favorable if possible (Scheme 7.48). The non-activated cumulated C=C bond of 340 takes part in the [4+ 2]-cycloaddition and hence the necessary reaction temperature is high. On the other hand, the progressive truncation of the tether and the electron deficiency of the allenic C=C bond involved give rise to a remarkable Diels-Alder reactivity of the sulfone 346 generated in situ from sulfoxide 345 [339]. 

Since the first reaction undoubtedly proceeds with inversion of configuration at sulfur, and since additional experiments demonstrated that the formation of chlorosulfurane 177 from sulfoxide 180 takes place with retention at sulfur, (5>chirality was assigned to (+>177. As for the designation of absolute configuration, Martin and Balthazor (195) proposed a system of nomenclature for optically active pentacoordinate species. 

Finally, it should be stressed that various nucleophilic and electrophilic reactions that lead from sulfoxides and sulfinates of known absolute configuration to new chiral tri- and tetracoordinate sulfur compounds and follow a stereochemically unambiguous course can be utilized for configurational assignments. Some of these reactions... 

Dialkyl and diaryl sulfoxides were reduced (deoxygenated) to sulfides by several methods. As a little surprise sulfides were obtained from sulfoxides by catalytic hydrogenation over 5% palladium on charcoal in ethanol at 80-90° and 65-90 atm in yields of 59-99% [684. In the case of p-tolyl -styryl sulfoxide deoxygenation was achieved even without reduction of the double bond giving 66% of p-tolyl -styryl sulfide and only 16% of p-tolyl -phenyl-ethyl sulfide [684],... 

In a similar manner, the methoxycarbonyl derivative (11) was generated from sulfoxide (119) and found to be an orange nonpolar product, although due to its extreme sensitivity to light and air, it could not be isolated. However, trapping experiments with N- phenylmaleimide led to the isolation of a mixture of endo/exo adducts (120) and (121 Scheme 35). The addition had occurred across the unsubstituted ring. 

Two violent pressure-explosions occurred during preparations of dimethylsulfinyl anion on 3—4 g mol scale by reaction of sodium hydride with excess solvent. In each case, the explosion occurred soon after separation of a solid. The first reaction involved addition of 4.5 g mol of hydride to 18.4 g mol of sulfoxide, heated to 70°C [1], and the second 3.27 and 19.5 g mol respectively, heated to 50°C [2]. A smaller scale reaction at the original lower hydride concentration [3], did not explode, but methylation was incomplete. Explosions and fire occurred when the reaction mixture was overheated (above 70°C) [4]. Reaction of 1 g mol of hydride with 0.5 1 of sulfoxide at 80°C led to an exotherm to 90°C with explosive decomposition [5]. These and similar incidents are explicable in terms of exothermic polymerisation of formaldehyde produced from sulfoxide by reaction with the hydride base [6]. The heat of reaction was calculated and determined experimentally. Thermal decomposition of the solution of hydride is not very violent, but begins at low temperatures, with gas evolution [7]. 

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