Sulfoxide, methyl methylthiomethyl

Carbanions formed from methyl methylthiomethyl sulfoxide 94 and ethyl ethylthio-methyl sulfoxide 95 were shown to be alkylated in excellent yields126,127. Treatment of 94 with rc-BuLi or KH and subsequent reaction with 1, n-dihalo- or bis(tosyloxy)alkane gave 3-, 4-, 5- and 6-membered 1-methylsulfmyl-l-methylthiocycloalkanes128"130. Upon hydrolyses of these products, the corresponding aldehydes and ketones are obtained. 

Sumiyoshi and coworkers studied the radiolysis of aqueous solution of methyl methylthiomethyl sulfoxide [ H3S(0) H2S H3 MTMSO] at various pH by pulse radiolysis. They found that the reaction of e with MTMSO (in the presence of 1M t-butyl alcohol to scavenge OH" radicals) leads to formation of a transient with a broad absorption band of = 375 nm. The absorbance at 375 nm as a function of pH are of S shape, indicating an equilibrium due to reaction with H. Similar to the finding in dimethyl sulfoxide they suggested the scheme. 

Use of methyl methylthiomethyl sulfoxide (6, 391-392) in place of TosMIC results in a difficultly separable mixture that fails to produce the dienone 3 on hydrolysis. 

Methyl 5-methoxy-3-oxopentanoate, 314 Methyl methylthiomethyl sulfoxide, 314 2-Methyl-5-nitroisoquinolinium iodide, 467 Methyl 2-nitrophcnyl disulfide, 314-315 2-Methyl-3-pentenoic acid, 65... 

Use of the chiral carbon pool for cyclopentenone preparation is also known. The fungal metabolite terrein [88] was selectively monoacetylated and then reduced with chromous chloride to enone [89]. Acetylation and olefin cleavage with ruthenium tetroxide aiwi sodium periodate led to aldehyde [90], which was readily decarbonylated to [65] (51). An alternative route (52) began with the less common S,S-tartaric acid [91], converted in four steps to diiodide [92]. Dialkylation of methyl methylthiomethyl sulfoxide with [92] gave the cyclopentane derivative [93]. Treatment of [93]... 

Cyclization of l,oi-dihalo [or bis(tosyloxy)] alkanes with methyl methylthiomethyl sulfoxide in the presence of a base such as Bu"Li or KH gave three-, four-, five- and six-memboed 1-methylsulfinyl-l-methylthiocycloalkanes that are easily converted to Ae corresponding ketone by acid hydrolysis. This is applicable to the formation of the key intermediate for the synthesis of isocaibacyclin, a potent prostacyclin analog. ... 

ALDEHYDES 1,3-Bis(methy lthio)ally 1-lithium. 2,4-Dimethylthiazole. Ethyl vinyl ether. Methyl methylthiomethyl sulfoxide. 2-Methyl-3-thiazoline. Nickel-aluminum alloy. Sodium tetracarbonylfer-rate(-II). 1,1,3,3-TetramethyIbutyl isocyanide. 2,4,4,6-Tetramethyl-5,6-dihydro-l,3-(4H)-oxazine. Thallium(III) nitrate. 

Methyl-methylthiomethyl-sulfoxid reagiert mit Grignard-Verbindungen in Tetrahydrofu-ran zu Dimethylthioacetalen, die z.B. mit Sulfurylchlorid/Silikagel/Wasser zu Aldehyden deacetalisiert werden konnen377 ... 

MMTS MsOH NBS NHMDS NMP NMR PPb Ph Pr PTC rt TBDMS Tf THF THP TLC TMEDA TMS TMSOTf Tol TOMAC Ts TsOH UDP methyl methylthiomethyl sulfoxide (=FAMSO) methanesulfonic acid N-bromosuccinimide sodium hexamethyldisililazide /V-methyl-2-pyrrolidone nuclear magnetic resonance parts per billion phenyl propyl Phase transfer catalysis room temperature t-butyldimethylsilyl triflatc (trifluoromethanesulfonate) tetrahydrofuran 2-tetrahydro-2//-pyran-2-yl thin-layer chromatography /V./V./V /V -tetramethylethylenediamine trimethylsilyl trimethylsilyl triflate p-tolyl trioctylmethylammonium chloride tosyl p-toluenesulfonic acid ultrasonically dispersed potassium... 

Cyclobutanones. Reaction of methyl methylthiomethyl sulfoxide with 1,3-dibromopropane in the presence of 2 eq. of potassium hydride leads to cyclo-butanone dimethyl dithioacetal S-oxide (2) in high yield. Intermediates (a)... 

Cycloalkanones Five- and six-membered cyclic ketones can also be prepared by reaction of methyl methylthiomethyl sulfoxide (1) and a 1, co-dihalo-( or ditosyloxy)alkane (2) in the presence of 2 eq. of base (potassium hydride or w-butyllithium) in THF at -70 to 20°. The product (3) is hydrolyzed to the ketone (4) by acid. Ogura et al. suggest that 2 eq. of base are required because... 

This reaction was used in a procedure for homologation of aromatic aldehydes, as illustrated for conversion of benzaldehyde into phenylacetaldehyde (5). The first step is a Knoevenagel-like reaction with methyl methylthiomethyl sulfoxide... 

CYCLOALKANONES Methyl methylthiomethyl sulfoxide. Diborane. Silver perchlorate. Sodium cyclopentadivinyldicarbonylferrate. 

CYCLOBUTANONES Methyl methylthiomethyl sulfoxide. Simmons-Smith reagent. 

The unsaturated ester 154 derived from D-glucose reacted stereospecifically with lithiated methyl methylthiomethyl sulfoxide to give the Michael s adduct... 

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