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Upstream product

• 70-18-8 GLUTATHIONE 
• 99-12-7 5-nitro-m-xylene 
• 1303610-42-5 3,5-Me₂C₆H₃-N(Teoc)OTBS 

Downstream Products

• 67083-40-3 1,3-dimethyl-5-nitrosobenzene 
• 1009639-10-4 N-(3,5-dimethylphenyl)acetohydroxamic acid 
• 1009639-12-6 8-[acetyl(3,5-dimethylphenyl)amino]-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxyguanosine 
• 1426845-71-7 8-[acetyl(3,5-dimethylphenyl)amino]-2'-deoxyguanosine 
• 1137726-81-8 C₅₃H₆₄N₉O₈P 

Relevant academic research and scientific papers

Polyfunctionalized biaryls accessed by a one-pot nucleophilic aromatic substitution and sigmatropic rearrangement reaction cascade under mild conditions

A practical synthetic method has been developed for polyfunctionalized biaryls based on a facile one-pot nucleophilic aromatic substitution (SNAr) reaction and [5,5]- or [3,3]-sigmatropic rearrangement reaction cascade. Under mild basic conditions, N-arylhydroxylamines reacted with o-activated fluoro (het)arenes to form N,O-diarylhydroxylamine intermediates which underwent spontaneously selective [5,5]-sigmatropic rearrangement reaction to produce diverse functionalized 4-amino-4′-hydroxy-1,1′-biaryls. A sequential SNAr reaction and [3,3]-sigmatropic rearrangement took place between N-arylhydroxylamines and 2-fluoropyridine derivatives or 4-fluorobenzonitrile to afford functionalized 2-amino-2′-hydroxy-1,1′-biaryls. As invaluable and unique building blocks, the resulting biaryls were applied in the straightforward synthesis of N2,O2-coronarene, carbazole, aza- and diaza carbazole derivatives.

Redox-Neutral Selenium-Catalysed Isomerisation of para-Hydroxamic Acids into para-Aminophenols

A selenium-catalysed para-hydroxylation of N-aryl-hydroxamic acids is reported. Mechanistically, the reaction comprises an N?O bond cleavage and consecutive selenium-induced [2,3]-rearrangement to deliver para-hydroxyaniline derivatives. The mechanism is studied through both 18O-crossover experiments as well as quantum chemical calculations. This redox-neutral transformation provides an unconventional synthetic approach to para-aminophenols.

Selective Photoinduced Reduction of Nitroarenes to N-Arylhydroxylamines

We report the selective photoinduced reduction of nitroarenes to N-arylhydroxylamines. The present methodology facilitates this transformation in the absence of catalyst or additives and uses only light and methylhydrazine. This noncatalytic photoinduced transformation proceeds with a broad scope, excellent functional-group tolerance, and high yields. The potential of this protocol reflects on the selective and straightforward conversion of two general antibiotics, azomycin and chloramphenicol, to the bioactive hydroxylamine species.

A general and scalable synthesis of polysubstituted indoles

A consecutive 2-step synthesis of N-unprotected polysubstituted indoles bearing an electron-withdrawing group at the C-3 position from readily available nitroarenes is reported. The protocol is based on the [3,3]-sigmatropic rearrangement of N-oxyenamines generated by the DABCO-catalyzed reaction of N-arylhydroxylamines and conjugated terminal alkynes, and delivers indoles endowed with a wide array of substitution patterns and topologies.

Synthesis of site-specific damaged DNA strands by 8-(acetylarylamino)- 2′-deoxyguanosine adducts and effects on various DNA polymerases

Beside the predominately found 8-(arylamino)-2′-dG, 8-(acetylarylamino) damages within DNA-strands may also play an important role in the induction of chemical carcinogenesis. A synthesis pathway leading to these 8-(acetylarylamino)-dG adducts using different aromatic amines has been optimized. The 8-modified dGs were converted into the corresponding phosphoramidites and site-specifically incorporated into different oligonucleotides leading to DNA strands. Lesion-bearing hybrids of these damaged DNA-strands with complementary oligonucleotides were used to study their melting properties and their circular dichroism spectra. It was shown that no EcoRI restriction took place with the damage inside the cleavage site. Finally, three different DNA polymerases were used for primer extension studies. C8-NAc-Arylamine adducts of 2′-deoxyguanosine with various aromatic amines were synthesized by using cross-coupling reactions and converted into 3′-phosphoramidites. Site-specific damaged NarI-, EcoRI- and 20mer-oligonucleotides were prepared by automated DNA-synthesis. Biophysical properties, restriction endonuclease studies and DNA-polymerase assays were performed. Copyright

Synthesis of N-arylhydroxylamines by Pd-catalyzed coupling

Pd-catalyzed coupling of aryl halides with TeocNHOTBS, followed by treatment of the products with TBAF, provides effective access to a wide range of N-arylhydroxylamines by a route that produces stable doubly-protected intermediates and allows the protective groups to be removed under mild conditions that do not cause extensive degradation of the final product.

A new short and efficient synthetic route to C8-N-acetylarylamine 2′-deoxyguanosine phosphoramidites

In addition to their C8-NH-arylamine-dG counterparts, C8-N-acetylarylamine adducts of 2′-deoxyguanosine (2′-dG) play an important role in the possible induction of chemical carcinogenesis. A new synthetic pathway of this adduct type using different aromatic amines has been developed following most probably an electrophilic amination reaction. These adducts can be converted into the corresponding phosphoramidites for incorporation into oligonucleotides. Georg Thieme Verlag Stuttgart.

Electrophilic intermediate in the reaction of glutathione and nitrosoarenes

A kinetic study is reported of the reaction of glutathione (γ-L-glutamyl-L-cysteinylglycine, GSH) with nine substituted nitrosobenzenes (3,4-Me2 4-Me, 3,5-Me2, 3-Me, parent, 3-MeO, 4-Cl, 3-Cl, 3-NO2). Previous workers have shown that this reaction proceeds in parallel pathways, producing the appropriate N-arylhydroxylamine and GSSG or a sulfinanilide adduct ArNHS(O)G; a rapid equilibrium addition to form a common intermediate, a semimercaptal ArN(OH)SG, has also been observed. In the present study, equilibrium constants for the formation of this intermediate from ArNO and GSH have been measured by a kinetic method, and the kinetic behavior of the slower additional reactions of the semimercaptal have been examined in detail. For experiments carried out at constant pH and buffer concentration, the decay of ArN(OH)SG follows the rate law k2GSH[GSH] + k2(rearr). A comparison with product ratios previously reported shows that the bimolecular term with GSH represents the process forming ArNHOH and GSSG, while the unimolecular term represents the rearrangement to the sulfmanilide. The former process is found to be proportional to [OH-] for solutions near neutrality, is not buffer catalyzed, and has a ρ value of +1.4. This suggests a mechanism in which glutathione anion GS- reacts at the sulfur of the adduct displacing ArN-(OH) as a leaving group. The rearrangement reaction follows σ+ with a ρ+ value of -3.5 and has a rate law containing a pH-independent term and terms for catalysis by H+ and the acid component of the buffer. An 18O tracer study shows that the S=O oxygen in the sulfmanilide is derived from solvent, not the original N=O group. A mechanism is proposed with rate-limiting N-O cleavage, either uncatalyzed involving direct heterolysis with OH- as a leaving group or catalyzed by acids with H2O as the leaving group. The species produced is a cationic intermediate ArN+SG, a nitrenium ion stabilized by both the aryl ring and the directly attached sulfur atom. Aryl-stabilized nitrenium ions are commonly encountered in Bamberger-like rearrangements of hydroxylamine derivatives. The sulfur atom of PhN(OH)SG is shown to provide an approximately 106 rate acceleration for N-O cleavage in a comparison with the Bamberger rearrangement of PhNHOH.

NMR Study of the Monomer-Dimer Equilibria of Dimethylnitrosobenzenes in Solution. Identification of Mixed Azodioxy Dimeric Species

The monomer-dimer equilibria of 2,6- and 3,5-dimethylnitrosobenzenes in CDCl3 solution were investigated by 1H and/or 13C NMR spectroscopy.The mixed systems nitrosobenzene + 2,6-dimethylnitrosobenzene and 2,6-dimethylnitrosobenzene + 3,5-dimethylnitrosobenzene were also studied, and mixed azodioxy dimers were identified.In all systems exchange occurs exclusively between dimer and monomer species, rates and activation energies being calculated from time-dependent 1H 1D spectra and/or 1H 2D-EXSY spectra measured at different temperatures. KEY WORDS 1H NMR 13C NMR 2,6-Dimethylnitrosobenzene 3,5-Dimethylnitrosobenzene Monomer-dimer equilibria Mixed azodioxy dimers