Methoxymethyl Phenyl Sulfide

We found that PhSCH2OCH3 can be lithiated completely within 45 min at temperatures between —40 and — 45 °C using n-BuLi in THF and hexane. Subsequent functionalizations gave high yields. When during the lithiation or derivatization reaction the temperature was allowed to rise above — 20 °C, however, reduced or low yields of impure products were obtained. Since reactions with most electrophiles can be completed within 1 to 2 hours at temperatures below — 40 °C, the lower stability of PhSCH(Li)OCH3 is not a serious drawback in syntheses performed on a small or moderate scale. Problems may arise if first an alkyl chain is introduced and the methyne proton in the product PhSCH(Alkyl)OCH3 is to be replaced by lithium. 1,3-Oxathiane has been incidentally used as a substrate for lithiation-functionalization reactions [4]. 

Fuji K, Ueda M, Sumi K, Fujita E (1981) Tetrahedron Lett 2005 

In their review, Grobel and Seebach [2] give a summary of the relative advantages and disadvantages of the use of S,S-acetals and the corresponding S-oxides in organic syntheses. 

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CSH10CIN 4-chloro-N,N-dimethyl aniline 698-69-1 504.15 44.283 1,2 13941 C8H10OS methoxymethyl phenyl sulfide 13865-50-4 453.82" 39.465 2... 

Treatment of 2-(phenylthio)alkanols (217), obtainable from methoxymethyl phenyl sulfide and ketones, with thionyl chloride affords the aldehydes (218) with rearrangement in high yields (Scheme 51). The cyclization of (218) to thiophenes (219) can be simply performed by stirring a solution of (218) with 2 equiv. of triethyloxonium tetrafluoroborate in dichloromethane. Although, in cases of R = Me, = Ph and R = Me, R = Ph, the formation of isomeric mixtures was expected, the reaction led to the predominant formation of the isomer (219) <85S434>. 

Mercapto- -2-sulfid E2, 709 2-Mercapto-4,4,5,5-tetramethyl- -2-sulfid E2, 710 2-(2-Methoxycarbonyl-phenoxy)- -2-oxid E2, 504 2-Methoxy-4-methoxymethyl- -2-sulfid XII/2, 647 2-Methyl- -2-oxid XII/1, 427 4-Methyl-2-phenoxy- -2-oxid E2, 604 4-Methyl-2-(2-phenyl-hydrazino)- -2-sulfid XII/2, 803... 

Amines (S)-1 -Amino-2-methoxymethyl-1 -pyrrolidine. Azidomethyl phenyl sulfide. Bis(methoxycarbonyl)sulfur diimide. N,N-Bis(trimethylsilyl)rnethoxymethylamine. 

In an analogous approach, the effect of imidazole was also observed by Inoue et al. [114]. When alkyl aryl sulfides were oxidized with a novel iron porphyrin catalyst (52) (0.2 mol% equiv), the reaction proceeded enantioselectively under appropriate conditions. Iodosobenzene was used as oxidant in dichloromethane at -43°C. The turnover number increases to 142, and an ee of 73% was obtained in the presence of a 100 to 600 molar ratio of imidazole to catalyst for the synthesis of (5)-methoxymethyl phenyl sulfoxide. In the absence of imidazole, the enantioselectivity disappeared, giving the racemic sulfoxide. 

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