Dimsyl anions

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

Methylsulfinyl enolates are more recently developed d -reagents. They are readily prepared from carboxylic esters and dimsyl anion. Methanesulfenic acid can be eliminated thermally after the condensation has taken place. An example is found in Bartlett s Brefeldin synthesis (P.A. Bartlett. 1978). 

Corey and Chaykovsky were the first to investigate the reaction of dimethyl sulphoxide anion (dimsyl anion) with aldehydes and ketones400,401. They found that the reaction with non-enolizable carbonyl compounds results in the formation of /1-hydroxyalkyl sulphoxides in good yields (e.g. Ph2CO—86%, PhCHO—50%). However, with enolizable carbonyl compounds, particularly with cycloalkanones, poor yields of hydroxyalkyl products are observed (e.g. camphor—28%, cyclohexanone—17%, but... 

In this way benzalaniline reacts with dimsyl anion to give /J-anilinosulphoxide 446 in 92% yield401 (equation 267). Nudelman and Cram have found that the analogous reaction with the carbanion of benzyl p-tolyl sulphoxide is more complex and leads to the formation of substituted cyclopropyl sulphoxides 447 (equation 268)522. The carbanion derived from cyclohexanone dimethyldithioacetal S-oxide 448 gives /J-mercaptoanilines derivatives on treatment with iminoketones and further elaboration523 (equation 269). 

The first reports on this reaction were published almost simultaneously by Russell and coworkers533 and Corey and Chaykovsky534, who reacted dimsyl anion with a variety of carboxylic esters and obtained the corresponding a-ketosulphoxides 464 in high yields (equation 277 Table 25). 

TABLE 25. Reaction of dimsyl anion with carboxylic esters... 

Reaction of dimsyl anion with isothiocyanates gives a-thioamidosulphoxides 478 in 12-59% yield, whereas with isocyanates it affords a mixture of a-amidosulphoxides 479 and methylsulphinylmalonoamides 480, the products of a double addition549 (equation 289). 

In contrast, a-ketosulphoxides react with isocyanates to give the products of a monoaddition only550 (equation 290). Reaction of dimsyl anion with trithiocarbonates 481 followed by alkylation results in the formation of (methylsulphinyl)ketene dithio-acetals 482551 (equation 291). 

Dimsyl anion 88 is known to add to styrene, and to 1,1-diphenylethylene in the presence of a base, forming 3-arylpropyl methyl sulfoxides121. Treatment of ( )-3,3-dimethyl thiacyclo-oct-4-ene-l-oxide 89 with n-BuLi gave exo-4,4-dimethyl-2-thiacyclo-[3.3.0]octane 2-oxide 90, a bicyclic addition product of the internal double bond. A similar cyclization was observed in the reaction of 91 with n-BuLi122. 

An interesting reaction of dimsyl anion 88 is the methylation of polyaromatic compounds. Thus naphthalene, anthracene, phenanthrene, acridine, quinoline, isoquinoline and phenanthridine were regiospecifically methylated upon treatment with potassium t-butoxide and DMSO in digyme or with sodium hydride in DMSO123-125. Since ca. 50% of D was found to remain in the monomethyl derivative 93 derived from 9-deuteriophenanthrene 92, the mechanistic route shown in Scheme 2 was suggested125. 

Dimsyl anion 88 reacts with esters of aromatic carboxylic acids and aliphatic acids which do not have a readily transferable proton, to give /5-ketosulfoxides114,133,138-141. There are not many cases in which acyl chlorides were used142,143. However, the reaction... 

Russell and coworkers147 had found that treatment of dimsyl anion 88 or of a similar methylsulfonyl carbanion with 1,2-, 1,3- and 1,4-dicarboxylic acid esters can give five- to seven-membered cyclic compounds. By this type of cyclization, they prepared ninhydrin hydrate 106 from diethyl phthalate148,149. 

Corey and Chaykovsky114 found that the dimsyl anion reacts with benzophenone and benzaldehyde to afford the corresponding /S-hydroxysulfoxides 109 and 110. Thermal decomposition of these j3-hydroxysulfoxides was shown to give a, )3-unsaturated sulfoxides155 or olefins156,157. Thus, the reaction of dimsyl anion with benzophenone at 100 °C gave 1,1-diphenylethylene, diphenylmethane, 1,1-diphenylcyclopropane and diphenylacetaldehyde, besides 1, l-diphenyl-2-methylthioethylene156,157. 

Dihydrodithiin sulphoxides, synthesis of 243 Dihydrothiophene dioxides, reactions of 653 /(,/( -Dihydroxyketones 619 Dimerization, photochemical 877, 884 Dimethyl sulphoxide anion of - see Dimsyl anion hydrogen bonding with alcohols and phenols 546-552 oxidation of 981, 988 photolysis of 873, 874, 988 radiolysis of 890-909, 1054, 1055 self-association of 544-546 Dimsyl anion... 

Polyaromatic compounds, reaction with dimsyl anion 607... 

Dccalin (decahydronaphthalene),benzene, 1,4-dioxane, and ethanol may be used as solvents for the photolysis. In an alternative procedure, volatile materials swept from the photolysis vessel are condensed in a dry ice trap. This cold mixture is added to a flask containing a magnetically stirred solution of dimsyl anion in dimethyl sulfoxide, and fractionation at reduced pressure provides a solution of bicyclopentene in tetrahydrofuran. 

Methane, mtro-, 55, 78 Methane, sulfinylbis-, ion(l-) [Dimsyl anion], 55, 18... 

Dimroth reflux condenser, 59, 20 Dimsyl anion, 55, 18 Dineopentyl sulfides, 58,146 Dinitrogen tetroxide, 56, 65... 

Chlorodiphenylphosphine 488 reacts with a-sulphinyl carbanions to give a-sulphinylphosphines 489 which undergo ready isomerization to a-sulphenylphosphine oxides 4W (equation 295). The report of Almog and Weissman that a-sulphinyl carbanions react with phosphorochloridates 491 to give a-phosphoryl sulphoxides 492 calls for correction (equation 296). Actually, the phosphorylation occurs at the oxygen atom of the ambident dimsyl anion, and is followed by the Pummerer-type reaction affording diethylphosphoric acid and tetraethyl pyrophosphate among other products . ... 

To obtain complete conversion of ketones to enolates, it is necessary to use aprotic solvents so that solvent deprotonation does not compete with enolate formation. Stronger bases, such as amide anion ( NH2), the conjugate base of DMSO (sometimes referred to as the dimsyl anion),2 and triphenylmethyl anion, are capable of effecting essentially complete conversion of a ketone to its enolate. Lithium diisopropylamide (LDA), which is generated by addition of w-butyllithium to diisopropylamine, is widely used as a strong... 

Preparation The dimsyl anion is generated from dimethylsulfoxide (DMSO) by use of base. The resulting lithio- or sodio- derivative is generally used in the DMSO solvent. 

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