Sulfoximide derivatives

The -substituted sulfoximide salt, CFjCFjCF2CF2S(0)=NLi, was treated with COCl to produce a disubstituted derivative [Ic]  

The isothiazole derivative, saccharin, in the presence of a quaternary ammonium salt, is converted into 3-chloro-l,2-benzisothiazole 1,1-dioxide c/. Section 10.2.2.2 [596]  

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Similar results were reported independently by Shingaki and coworkers for the S, S-dimethyl-Af-ethoxycarbonyl sulfimide analogs. The photolysis of the higher valent sulfoximide derivatives, ArS02N=S(0)Me2, had earlier been reported by Abramovitch and Takaya ° not to yield the expected sulfonylnitrene but instead to give products arising... 

Finally, it should be noted that in contrast to optically labile sulfonium ylides, the oxosulfonium yUdes derived from chiral sulfoximides and related compounds are configurationally stable. Johnson and co-workers (184) have obtained a large number of chiral oxosulfonium ylides having the general structures 161 and 162 and have used them as nucleophilic alkylidene transfer agents for asymmetric synthesis. These results are discussed in the last part of this chapter. 

IB For a review of sulfoximides R2S(0)NR3 and ylides derived from them, see Kennewcll Taylor Chem. Soc. Rev. 1980, 9, 477-498. 

Direct amination of quinoxalinones with hydroxylamine-O-sulfonic acid produces the 1-amino derivatives (135) in 70-80% yield, and subsequent oxidation with lead tetraacetate gives the 1,2,4-benzotriazines (138). Benzotriazine formation probably involves the formation of an intermediate nitrene (136), ring expansion to a benzo-triazepinone (137) and subsequent loss of carbon monoxide. The nitrene (136 R = Ph) was trapped as the sulfoximide 139 when the oxidation was carried out in the presence of dimethyl sulfoxide.147... 

The cis- and frans-sulfoxides (551) and (552) have been O-methylated with Meerwein s reagent. Reaction of the methoxy derivative with MeMgBr proceeds with inversion of configuration (Scheme 211) (74JA8026). The stereochemical course of the interconversions of sulfoxide, sulfimide and sulfoximide in the 2,3-dihydrobenzo[6]thiophene series has been investigated (73JA1916). The reaction cycle (Scheme 212) involves both nucleophilic and electrophilic substitution at chiral sulfur. Inversion of configuration takes place in the conversion of (553) to (554) in pyridine. 

Perfluorotetramethylene sulflmides are synthesized by the reaction of lithium amide and pnmary amines with (perfluorotetramethylene)sulfur difluonde [7(5] (equation 13) (Table 6) The products can be oxidized with m-chloroperoxybenzoic acid to the corresponding sulfoximides (equation 13) or can be treated with chlorine or bromine to yield N-halo derivatives [76] The reaction of CF3SF3=NCF3 with nucleophiles takes place by attack of the nucleophile at the positive sulfur center [17] (equation 14)... 

Similarly, the cycloaddition of chiral thiocarbonyl 5-oxides, derived From optically active TV-substituted 5-phenyl- or S-(4-methylphenyl)-5-(l-trimethylsilylethyl)sulfoximides with 2,3-di-methyl-1,3-butadiene, is completely stereoselective affording TV-substituted 3,6-dihydro-2,4,5-tri-methyl-2-[(5)-5-phenyl- or 5-(4-methylphenyl)sulfonimidoyl)]-2//-thiopyran 1-oxides as single diastereomers, determined by 1H-NMR spectroscopy using shift reagents and analytical reverse-phase HPLC85,87. 

The chemistry of sulfoximides (sulfoximines) is somewhat related to that of sulfones. - - Although several methods are available for the preparation of free sulfoximines from di- and tri-valent sulfur compounds, the methods are of limited applicability when the desired sulfoximines contain labile functional groups. An alternative approach involving alkylating the readily available anion derived from N-suh-stituted methylsulfoximides has been described but preparation of the free sulfoximides has proved... 

Williams and Cram47 prepared the cyclic sulfoximide 62, with a chiral sulfur atom, in three steps from 2-methylthio-5-methylacetophenone (59). The latter compound was converted into a 2-methylthiophenylacetic acid derivative (60), which was then oxidized to the 2-methylsulfinyl compound 61. Compound 61 was cyclized to 62 in 60% yield using sodium azide in sulfuric acid (Eq. 14).48... 

Stoss has reported51 antisecretory activity for sulfoximides (64) derived from l,2-benzothiazin-3-ones. 

The S-oxides 2 and 4 are stable, crystalline compounds with tetrahedral configuration comparable to cyclic sulfoximides. The compounds are derivatives of iminosulfonamides or iminosulfuric acid diamides, respectively.23... 

The imidazo[5,l -e]-l.2,3,5-Letrazine-8-carbonyl chloride 17 reacts preferentially with nucleophiles (Nu ) at the 8-carbonyl group rather then at the 4-oxo group, allowing the preparation of a wide range of ester, thioester, amide, hydroxamic acid, hydrazide, sulfoximide, azide, and diazoacetyl derivatives.42... 

The same cyclopropane derivative was also obtained by the reaction of chalcone with (+)-S-methyl-S-phenyl-N-(p-tolyl)sulfoximide and tert. BuOK at room temperature in 94% yield (Scheme 43). 

Sulfoxides are oxidized to sulfoximides by HN3 in the presence of H2SO4 [1, 19]. The nucleophilic substitution of chloride by azide is accelerated, when the solution of HN3 and alkyl halide is allowed to react in a column filled with acidic AI2O3 [20]. The exchange of halide substituents of arenes by azide requires activating groups in other positions of the aromatic system. Pyridine derivatives frequently yield tetrazoles [8]. Aromatic C-nitroso compounds and twice the molar quantity of HN3 form the aromatic azide, N2, and H2O... 

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