Nitro-phenylsulfonyl

Directed osmylation.J One step in a synthesis of the carbonucleoside aris-teromycin (3) required dihydroxylation of the intermediate 1, in which a (nitro-phenylsulfonyl)methyl group is used as a carboxy equivalent. The desired diol (2)... 

Several fluoro analogs of ketoses have been reported 1,6-dideoxy-1,6-difluoro-D-fructose was readily obtained from 2,3-O-isopropyli-dene-l,6-di-0-p-tolylsulfonyl-)3-D-fructofuranose by treatment with potassium fluoride in 1,2-ethanediol under a stream of carbon dioxide.96 Surprisingly, although the 6-sulfonyloxy group would be expected to be more reactive than the 1-sulfonyloxy group,97-99 no selectivity was observed. The failure to obtain 1-deoxy-l-fluoro-D-fructopyranose96 from 2,3 4,5-di-0-isopropylidene-l-0-(methylsulfonyl) (or p-nitro-phenylsulfonyl)-/3-D-fructopyranose or phenyl 3,4,5-tri-O-acetyl-l-O-(methylsulfonyl)-/3-D-fructopyranoside by treatment with potassium or sodium fluoride in 1,2-ethanediol, N,N-dimethylformamide, or form-amide at elevated temperatures may be attributed to the fact that nu-... 

Die Michael-Addition von Nitro-ethan an a-jS-ungesattigte Sulfone mit Kaliumfluorid und einem Alkaloid-Hydrohalogenid, z. B. (17 .2.S )-N-Benzyl-N-methyl-ephedriniumbro-mid in einem Zwei-Phasen-System fuhrt zu Nitro-phenylsulfonyl-alkanen1 z. B. ... 

Cyclopentan 2,3-Dihydroxy-l-(nitro-phenylsulfonyl-methyl)- E2le, 4566 (En - 1,2-Diol)... 

Ethoxycarbonylamino)cyclohcxanoncs were obtained in low yield by hydrolysis of the aziridines formed by the addition of ethoxycarbonyl nitrene, generated in situ from 4-nitro-phenylsulfonyl carbamates, to enamines prepared from substituted cyclohexanones61,62. By the same method, optically active 2-(ethoxycarbonylamino)cyclohexanone 3 was prepared in low yield from the enamine 1 derived from an optically active 2-substituted pyrrolidine63. 

Acetyl-6-(p-nitrophenylthio)-4(l//)-cinnolinone (14) gave 3-acetyl-6-(p-nitro-phenylsulfonyl) (l//)-cinnolinone (14a) (substrate, AcOH, 30% H202i... 

The DA reaction of frani-l-nitro-2-phenylsulfonylethy-lene (4a) [13] with 1,3-cyclohexadiene occurred smoothly at 60 °C to give nitro phenylsulfonyl bicyclo[2.2.2]octene 6a [14] (Table 15.1), which was then subject to desulfony-lation with DBU followed by the Barton-Zard reaction to... 

The 3-substituents in 3-nitro- and 3-phenylsulfonyl-2-isoxazolines were displaced by a variety of nucleophiles including thiolate, cyanide and azide ions, ammonia, hydride ions and alkoxides. The reaction is pictured as an addition-elimination sequence (Scheme 54) (72MI41605, 79JA1319, 78JOC2020). 

Thiophene, 3-nitro-4-(phenylsulfonyl)-cine substitution, 4, 817, 825 Thiophene, oxo-synthesis, 4, 125... 

The transformation of l-methylthio-l-(methylsulfonyl)alkanes (254) to methyl esters can be efficiently carried out by oxidation or by a-chlorination followed by methanolysis (equation 152)145. The lithium or the sodium salt of (phenylsulfonyl)nitromethane (256) is a very useful reagent for the preparation of higher homologues of nitromethanes by alkylation since the salts are air insensitive, non-hygroscopic, and easily handled without decomposition. The oxidation of the resulting secondary a-nitro sulfone (257) gives... 

Phenyl- 50, 55, 398, 514, 522, 581, 633, 645ff. 2-Phenyl-l-(2-hydroxylamino-phenyl)- 698 2-Phenyl-1 -(2-nitro-phenyl)- 698 2-Phenyl-1 -(2-nitroso-phenyl)- 698 2-Phenyl- -sulfinsaure 461 2-Phenyl- -sulfonsSure-chlorid 461 2-Phenylsulfonyl-1,1 -diphenyl- 634 Phenylsulfonyl-triphenyl- 464 Tetraaryl-... 

Phenylsulfonyl)nitromethane is preferentially C-alkylated by ally lie acetates in the presence of Pd(PPh3)4 (5 mol%) to give various a-nitro sulfones as shown in Eq. 5.53.76... 

It has been known that aromatic heterocycles such as furan, thiophene, and pyrrole undergo Diels-Alder reactions despite their aromaticity and hence expected inertness. Furans have been especially used efficiently as dienes due to their electron-rich properties. Thiophenes and pyrroles are less reactive as dienes than furans. But pyrroles with A-elecIron-withdrawing substituents are efficient dienes. There exists a limited number of examples of five-membered, aromatic heterocycles acting as dienophiles in Diels-Alder reactions. Some nitro heteroaromatics serve as dienophiles in the Diels-Alder reactions. Heating a mixture of l-(phenylsulfonyl)-3-nitropyrrole and isoprene at 175 °C followed by oxidation results in the formation of indoles (see Eq. 8.22).35a A-Tosyl-3-nitroindole undergoes high-yielding Diels-Alder reactions with... 

In 4-Nitro-7-phenylsulfonyl-benzofurazan gelingt der Austausch der Nitro- gegen eine Meth-oxy-Gruppe mit Natriummethanolat in analoger Weise erhalt man aus 4,7-Bis-[4-methyl-phe-nylsulfonyl]-benzofurazan mit Natriumazid in DMF 7-Azido-4-(4-methyl-phenyl-sulfonyl)-ben-zofurazan88. 

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