A- sulfonium salts

Sulfur ylides contain a carbanion, which is stabilizea oy an adjacent positively-charged sulfur. Ylides derived from alkylsulfonium salts are usually generated and utilized at low temperatures. Oxosulfonium ylides are, however, stable near room temperature. The most common method of ylide formation is deprotonation of a sulfonium salt. What has been said... 

Several variations of the Feist-Benary reaction furnish substituted furans as products. The following three examples provide synthetically useful alternatives to the standard reaction conditions. One method is based on the reaction of a sulfonium salt with a P-dicarbonyl compound. For example, reaction of acetylacetone (39) with sulfonium salt 38 in the presence of sodium ethoxide yields 81% of trisubstituted furan 40. This strategy provides a flexible method for the preparation of 2,3,4-trisubstituted furans. 

The ionic species 5, as well as 6, represent the so-called activated dimethyl sulfoxide. Variants using reagents other than oxalyl chloride for the activation of DMSO are known. In the reaction with an alcohol 1, species 5, as well as 6, leads to the formation of a sulfonium salt 7 ... 

In an attempt to prepare sulfonium-ylide polymer, Tani-moto and coworkers [57,58] carried out the reaction of a sulfonium salt polymer with benzaldehyde in the presence of a base and obtained styrene oxide. The reaction was considered to process via a ylide polymer formation (Scheme 24), which may be unstable and has not been isolated. 

Ajoene (Spanish, ajo, garlic), 4,5,9-trithiadodeca-l,6,ll-triene-9-oxide 35 (Scheme 12), an antithrombotic compound with other well-defined physiological properties, is formed from allicin.84 Like allicin, ajoene is a sulfoxide but has two further sulfur atoms in a disulfide linkage. E and Z isomeric forms are possible involving the C=C bond at positions 6 and 7. Ajoene is somewhat more stable than allicin. The formation of ajoene probably involves condensation of 2 molecules of allicin forming a sulfonium salt 33, with elimination of propenesulfenic acid. Elimination of a second molecule of propenesulfenic acid... 

The Cu(I)-catalyzed cyclization for the formation of ethyl ( )-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate 82 has been accomplished starting from propargyl alcohol and ethyl 2-phenylsulfonyl cinnamate. Upon treatment with Pd(0) and phenylvinyl zinc chloride as shown in the following scheme, the methylenetetrahydrofuran 82 can be converted to a 2,3,4-trisubstituted 2,5-dihydrofuran. In this manner, a number of substituents (aryl, vinyl and alkyl) can be introduced to C4 <00EJO1711>. Moderate yields of 2-(a-substituted N-tosyIaminomethyl)-2,5-dihydrofurans can be realized when N-tosylimines are treated with a 4-hydroxy-cis-butenyl arsonium salt or a sulfonium salt in the presence of KOH in acetonitrile. The mechanism is believed to involve a new ylide cyclization process <00T2967>. 

A simplistic view of the mechanism is depicted in Scheme 3.5. The sulfoxide (I) is activated by triflic anhydride to generate a sulfonium salt (III). It was observed early on that the outcome of the glycosylation was not influenced by the configuration at the two variable stereogenic centers in the sulfoxide donor (i.e., anomeric carbon and sulfur).1 This was taken as evidence for the intermediacy of the oxycarbenium ion (V), which arises from rapid elimination of an alkylsulfenyl triflate(IV) from III. Reaction of V with a nucleophile then gives rise to a mixture of a- and P-glycosides (II). 

Mislow and his co-workers (261) suggested, however, that epimeriza-tion of menthyl sulfinates occurs via either a sulfurane intermediate 221 or a sulfonium salt 222. 

Nitrogen tetroxide also causes rapid racemization of sulfoxides however, the reaction takes place without decomposition (279,280). This process is initiated by the formation of a sulfonium salt, which then undergoes partial ionization to form a dication intermediate. 

The thermal S-dealkylation of benzothiazine ylides was shown in Scheme 11 and the dealkylation of a sulfonium salt in Scheme 37. All other reported reactions involve N-substituents. 

Full transition from one linear behavior to the other requires no less than 0.7 V. In the framework of detecting a mechanistic change, the temperature effect on the potential dependence of a is very important. By studying the reduction of the 4-acetyl perbenzoate, it has been shown that the transition is shifted toward a stepwise pattern by lowering the temperature and thus by shifting the voltammetric peak closer to °ab/ab nd away from °ab/a, b--A similar observation has been reported for the reduction of a sulfonium salt... 

Interaction with diethyl sulfide occurs with simultaneous elimination of nitrogen and formation of a sulfonium salt of type 306 its hydrolytic decomposition yields 5-hydroxy- (307) and 5-ethylthio-3-phenyl-l,2,4-thiadiazole (308), in proportions dependent upon the hydrogen ion concentration of the medium.160... 

The problem of oxidative phosphorylation has been approached through model studies that utilize the phosphorylating potential of metaphosphate. In the mitrochondrial process inorganic phosphate and adenosine diphosphate are converted to adenosine triphosphate. Wieland, in a series of papers (e.g. ref. 31), has shown that a variety of thiolactones can activate inorganic phosphate in the presence of bromine for transfer to adenosine diphosphate (ADP). The intermediate may be an acyl phosphate or a sulfonium salt similar to that postulated by Higuchi and Gensch32 and by Lambeth and Lardy33, viz. 

The Pummerer reaction of sulfinyl compounds involves the formation of an a-functionalized sulfide [244, 245] from a sulfoxide. Acetic anhydride is commonly used as the electrophile, which adds to the sulfoxide to yield a sulfonium salt, and the rearrangement occurs through successive formations of an ylide (rate-determining step) and an alkylidene sulfonium, trapped by a nucleophile, or stabilized by a proton loss with formation of a vinyl sulfide. 

Methionine 13 in S-peptide has been modified by oxidation to the sul-fone or by conversion to a sulfonium salt with either iodoacetic acid or iodoacetamide (138). There is a dramatic lowering of the peptide-protein binding constant for all of the derivatives, but the complexes when formed appear to have nearly normal catalytic activity. The X-ray structure does not appear to permit the normal sulfur location with the sulfonium salts. Sterically, Met 13 can be moved by rotation about the carbon a-carbon / bond so that the residue sticks out into the solvent. This can be done without any major change in the conformation of the rest of the peptide. Thus the active site could be maintained undisturbed while the contribution of Met 13 to the S-peptide S-protein association would be lacking. 

Dimethyl sulfide, generated from DMSO, attacks the enone resulting from the oxidation of the alcohol. A sulfonium salt is generated that decomposes into a sulfur-containing side-compound. Performing the oxidation entirely at 78 C, prevents the undesired attack of... 

The selenium analogue of salacinol 110 has been prepared. Salacinol is a sulfonium-salt glucosidase inhibitor. This analogue shows at best only weak biological activities relative to the parent sulfonium salt <2004JA12458>. 

The positive charge carried by the sulfur atom means that the protons next to the sulfur atom in a sulfonium salt are significantly more acidic than those in a sulfide, and sulfonium salts can be depro-tonated to give sulfonium ylids. 

The first step is just the SN2 displacement of Cl- by RS that you have already seen. The second step actually involves chlorination at sulfur (you have also seen that sulfides are good soft nucleophiles for halogens) to form a sulfonium salt. Now a remarkable thing happens. The chlorine atom is transferred from the sulfur atom to the adjacent carbon atom by the Pummerer rearrangement. 

The generally accepted mechanism6 of Pummerer rearrangement is the one in which there is an initial attack on the sulfoxide oxygen atom by an electrophilic species, e.g., protonation or acylation. Acylation is followed by proton abstraction by a base from the a-carbon atom of the sulfoxide to form an ylide, which rapidly eliminates an acetate anion to form the a-sulfonium salt. Addition of acetate anion to the sulfonium intermediate completes the formation of the a-functionalized sulfide. Ylide formation from sulfoxonium salts is well recognized, and this aspect... 

Reaction with an alkyl halide to yield a sulfonium salt (Sec. 18.8)... 

In an earlier investigation by the author [ 1 ] a sulfonium salt pair, (I), was used as a chemical amplification type resist that utilized the catalytic action of an acid generated from a sulfonium salt. In a subsequent investigation by Kamabuchi [2] an acid generator salt pair, (II), was prepared and was effective as a chemical amplification type positive resist. 

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