Phenylthio nitromethane

Deprotection of the 5 -phosphate is easily accomplished after oxidative treatment. Oxidation with sodium metaperiodate in water (or in 0.1 M triethylammonium bicarbonate) gives the corresponding sulfoxide derivative. The free nucleotide is hberated by treatment with 2 M aqueous sodium hydroxide at room temperature (eq 2). Alternatively, the sulfide is oxidized to suhbne with NCS in 0.1 M triethylammonium bicarbonate buffer at room temperature. In this case, deprotection can be achieved successfully 

Takashi Sugimura Himeji Institute of Technology, Hyogo, Japan 

Preparative Method most conveniently prepared by reaction of the sodium salt of nitromethane with benzenesulfenyl chloride.  

Handling, Storage, and Precautions may be stored essentially unchanged in a freezer at —25 °C unpleasant odor best handled in a well-ventilated hood any spillage may be cleaned up with commercial bleach. 

Nitroalkene Synthesis. Henry reaction of (phenylthio)nitro-methane with aldehydes fohowed by dehydration has been used to prepare (. -l-nitro-l-phenylthioalkenes. potassium 7eri-butoxide-catalyzed addition and dehydration via mesylation (eq 1), or direct condensation catalyzed by piperidinium acetate (eq 2), are the methods of choice. Henry reaction can be also carried out by reaction of the nitroalkene dianion with aldehydes.  

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Seebach s procedure. Alternatively, (phenylthio)nitromethane may be prepared... 

Anthony G. M. Barrett, Dashyant Dhanak, Gregory G. Graboski, and Sven J. Taylor 8 (PHENYLTHIO)NITROMETHANE... 

PhenyUhlo)nltroinethane Is a convenient reagent for the synthesis of derivatives of 3-methylfuranfor the preparation of a-subst1tuted phenylthio esters via the homologation of aldehydes, and for the preparation of bicycllc g-lactams from monocyclic precursors/ This method 1s an adaption of Seebach s procedure/ Alternatively, (phenylthio)nitromethane may be prepared... 

The most recent entry to bicyclic P-lactam compounds through this approach, has been introduced by Barrett and his coworkers [120] by using an intramolecular Michael type reaction of a Af-silyl p-lactam to a nitroalkene induced by fluoride ion (Scheme 45). Namely, the known P-lactam 299 [32a] readily prepared from CSI addition to 1,5-hexadiene, was protected by using TBDMSCI and DIPEA to produce the p-lactam 300. Subsequent ozonolysis, gave the aldehyde 301. Henry reaction of the aldehyde 301 with (phenylthio)-nitromethane furnished, after dehydration of the resulting nitroaldol, the nitroalkene 302 which smoothly cyclized to the carbapenam 303 in the presence of... 

Triethylamine added to a soln. of (phenylthio)nitromethane, 1-hexene, and phenyl isocyanate in benzene, the mixture stirred at 25° for 30 min, and heated at 45° for 12 h 5-butyl-4,5-dihydro-3-(phenylthio)isoxazole. Y 80%. F.e. and oxidation to 3-sulfonyl-AMsoxazolines s. D.P. Curran, J.-C. Chao, J. Org. Chem 53 5369-71 (1988). 

The adducts of cyclic ketones and (phenylthio)nitromethane undergo ring expansion to provide 2-(phenylthio)cycloalkanones on aluminum chloride-mediated denitration. ... 

Phenylthio)nitromethane is useful in polyoxin synthesis. A ribose nitroalkene (2), derived from (phenylthio)nitromethane and the corresponding aldehyde (93%), was found to react with opposite stereochemical biases with potassium trimethylsilanoate (eq 5) and phthalimide (eq 6) followed by ozonolysis. The hydroxy acid (eq 5) was further transformed into polyoxin C. 

The Michael addition of (phenylthio)nitromethane to a steroidal enone and nitro displacement (eq 12) has been employed in the stereoselective 16-methylation of corticosteroids. ... 

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