Methyl 5-thio sulfone

If greater activation is desired the methyl- or aryl-thio derivatives may be oxidized to the sulfoxides/sulfones (Section 2.15.4.1), which may then be aminated (64JOC2903, 80JOC3746, 77JOC997). 

Cefonicid Cefonicid, 7-D-mandelamido-3-[[(l-sulfomethyl]-l/f-tetrazol-5-yl]thio] methyl]-8-oxo-5-thia-l-azabicyclo[4.2.0]oct-2-en-2-carboxylic acid (32.1.2.26), is structurally similar to cefamandole and differs in the presence of a sulfonic acid group in the methyl substituent of the tetrazol ring. It is synthesized by a method analogous to that of the synthesis of cefamandole [120-123],... 

M. Shi and Y.-L. Shi reported the synthesis and application of new bifunctional axially chiral (thio) urea-phosphine organocatalysts in the asymmetric aza-Morita-Baylis-Hillman (MBH) reaction [176, 177] of N-sulfonated imines with methyl vinyl ketone (MVK), phenyl vinyl ketone (PVK), ethyl vinyl ketone (EVK) or acrolein [316]. The design of the catalyst structure is based on axially chiral BINOL-derived phosphines [317, 318] that have already been successfully utilized as bifunctional catalysts in asymmetric aza-MBH reactions. The formal replacement of the hydrogen-bonding phenol group with a (thio)urea functionality led to catalysts 166-168 (Figure 6.51). 

Methyl-2,4,6-triphenyl-2f/-thiopyran (2461) reacts with hydrogen peroxide in acetic acid to produce sulfoxide 411,39 whereas condensed 2//-thio-pyrans 412 and 414 gave the corresponding sulfones 413100 and 415,368 respectively. 

Methyl 3,5-anhydro-3-thio-/3-D-xylofuranoside was oxidized with hydrogen peroxide to a mixture of the endo-sulfoxide, the -sulfoxide and the sulfone. Only the methyl 3,5-anhydro-3-thio-/ -D-xylofuranoside. V,.V-dioxidc could be isolated from the mixture by column chromatography in the pure crystalline form in 34% yield <2004CAR1787>. Treatment of spirocyclic thietane 25 (R = Me) with 2 equiv of w-chloropcrbcnzoic acid (MCPBA) yielded the sultine 30 in 54% yield (Equation 6) <1999J(P1)1151, 2002HCA2383>. 

Methylation of the 2-thio analogue of xanthine (129) at 170 °(i gave a quaternary salt which with ammonia afforded the betaine (130) in which both 5- and A-methylation has occurred. The analogous compound (131) is similarly produced as a toluene-4-sulfonate salt from 2-amino-6-thioxo-l,6-dihydropurine and methyl toluene-4-sulfonate (62JA1914). 

A more satisfactory synthesis of compounds of this type has been achieved by use of sulfonic esters. Thus, methyl 4,6-0-benzylidene-3-O - (methyl sulfonyl) - 2 - S - phenyl - 2 - thio - a - D - altropyranoside gave methyl 4,6-0-benzylidene-3-deoxy-2-S-phenyl-2-thio-a-D-ert/ hro-... 

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