- NITROSATION REAGENTS AND METHODS
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Provided are compounds that can find use as nitrosation reagents. Provided are nitrosation methods that include reacting a substrate with one of the provided nitrosation reagents and thereby generating a nitrosation product. Provided are kits including a nitrosation reagent. Provided are compositions wherein the nitrosation reagent is enriched in the 15N isotope.
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Paragraph 00182; 00183; 00202-00205; 00210-00213; 00351
(2022/02/06)
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- Versatile new reagent for nitrosation under mild conditions
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Here we report a new chemical reagent for transnitrosation under mild experimental conditions. This new reagent is stable to air and moisture across a broad range of temperatures and is effective for transnitrosation in multiple solvents. Compared with traditional nitrosation methods, our reagent shows high functional group tolerance for substrates that are susceptible to oxidation or reversible transnitrosation. Several challenging nitroso compounds are accessed here for the first time, including 15N isotopologues. X-ray data confirm that two rotational isomers of the reagent are configurationally stable at room temperature, although only one isomer is effective for transnitrosation. Computational analysis describes the energetics of rotamer interconversion, including interesting geometry-dependent hybridization effects.
- Galloway, Jordan D.,Sarabia, Cristian,Fettinger, James C.,Hratchian, Hrant P.,Baxter, Ryan D.
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supporting information
p. 3253 - 3258
(2021/05/06)
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- Bioorthogonal Click and Release Reaction of Iminosydnones with Cycloalkynes
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We report the discovery of a new bioorthogonal click-and-release reaction involving iminosydnones and strained alkynes. This transformation leads to two products resulting from the ligation and fragmentation of iminosydnones under physiological conditions. Optimized iminosydnones were successfully used to design innovative cleavable linkers for protein modification, thus opening up new areas in the fields of drug release and target-fishing applications. This click-and-release technology offers the possibility of exchanging tags on proteins for functionalized cyclooctynes under mild and bioorthogonal conditions.
- Bernard, Sabrina,Audisio, Davide,Riomet, Margaux,Bregant, Sarah,Sallustrau, Antoine,Plougastel, Lucie,Decuypere, Elodie,Gabillet, Sandra,Kumar, Ramar Arun,Elyian, Jijy,Trinh, Minh Nguyet,Koniev, Oleksandr,Wagner, Alain,Kolodych, Sergii,Taran, Frédéric
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supporting information
p. 15612 - 15616
(2017/12/02)
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- Sydnone Cycloaddition Route to Pyrazole-Based Analogs of Combretastatin A4
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The combretastatins are an important class of tubulin-binding agents. Of this family, a number of compounds are potent tumor vascular disrupting agents (VDAs) and have shown promise in the clinic for cancer therapy. We have developed a modular synthetic r
- Brown, Andrew W.,Fisher, Matthew,Tozer, Gillian M.,Kanthou, Chryso,Harrity, Joseph P. A.
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p. 9473 - 9488
(2016/11/11)
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- 4-Halogeno-sydnones for fast strain promoted cycloaddition with bicyclo-[6.1.0]-nonyne
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New sydnone derivatives have been synthesized and screened for their capacity to undergo fast copper-free cycloaddition reaction with bicyclo-[6.1.0]-nonyne. The influences of substitution in positions N-3 and C-4 of sydnones have been particularly studied leading to the identification of highly reactive partners for bio-orthogonal ligation reactions.
- Plougastel, Lucie,Koniev, Oleksandr,Specklin, Simon,Decuypere, Elodie,Créminon, Christophe,Buisson, David-Alexandre,Wagner, Alain,Kolodych, Sergii,Taran, Frédéric
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supporting information
p. 9376 - 9378
(2014/08/05)
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- Synthesis of 2 H-indazoles by the [3 + 2] dipolar cycloaddition of sydnones with arynes
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A rapid and efficient synthesis of 2H-indazoles has been developed using a [3 + 2] dipolar cycloaddition of sydnones and arynes. A series of 2H-indazoles have been prepared in good to excellent yields using this protocol, and subsequent Pd-catalyzed coupl
- Fang, Yuesi,Wu, Chunrui,Larock, Richard C.,Shi, Feng
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experimental part
p. 8840 - 8851
(2012/01/02)
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- Zwitterionic and mesoionic liquids: Molecular aggregation in 3-methylsydnone
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Ionic liquids are green solvents with interesting properties: displaying low melting points and high boiling points. They offer a new approach applicable in many instances. Nevertheless, the presence of free ions can be a matter in some cases, e.g. for the study of nucleophilic reactions, in electrochemistry, and in each situation where there is a competition between counter ions, as in micellization of ionic surfactants. Neutral compounds having formal unit electrical charges of opposite sign, and the same physical properties than ionic liquids would be a nice alternative to these latter solvents. There are two classes of chemical compounds having these characteristics: zwitterionic liquids (with no uncharged canonical representation) and mesoionic liquids (in which the negative and the positive charges are delocalized). In that last class we have chosen to work with 3-methylsydnone in order to examine, in this aprotic solvent, if it was possible to observe aggregation of surfactants in the same manner as in water. With all kinds of surfactants studied (ionic, zwitterionic and mesoionic) we have been able to demonstrate the formation of direct micelles: hydrogen bonding is thus not mandatory for molecular aggregation. Comparison of the behavior in water and in formamide showed that solvophobic interactions were qualitatively comparable but with a lower intensity.
- Cassel, Stephanie,Rico-Lattes, Isabelle,Lattes, Armand
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experimental part
p. 2063 - 2069
(2011/03/17)
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- Reactivity of nitrogen nucleophiles towards S-nitrosopenicillamine
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We report the results of a kinetic study of the reactions of a number of nitrogen nucleophiles with the nitrosothiol S-nitrosopenicillamine (SPEN). The range of nucleophiles includes primary, secondary and tertiary aliphatic amines, together with hydrazine, hydroxylamine, azide ion, ammonia, semicarbazide, thiomorpholine and S-methylcysteine. Secondary amines form N-nitrosamines quantitatively. As expected, reaction occurs via the free base forms of the nucleophiles and consequently most of the reactions take place readily only at relatively high pH. Experiments were carried out with [nucleophile] ? [RSNO], and for many reactions, plots of the first order rate constant vs. [nucleophile] were linear. For ammonia and the primary amines, however, this plot tended to level off at high [nucleophile] and an explanation is offered involving the reversible formation of an inactive RSNO-amine complex, for which there is spectral evidence, in parallel with the main reaction. For the secondary amines there is a reasonably good Broensted plot with a β value of ~0.2. The much greater reactivities of S-methylcysteine and thiomorpholine, compared to those of primary amines and morpholine respectively are consistent with initial attack at the sulfur atom, followed by an internal rearrangement. Over the whole range of nucleophiles studied there is a reasonable correlation with the Ritchie N+ parameter, and not with the Pearson n scale. Comparisons are made with the corresponding reactions of alkyl nitrites and N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS).
- Munro, Andrew P.,Williams, D. Lyn H.
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p. 1989 - 1993
(2007/10/03)
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- Synthesis and reactions of 9,10-diazatetracyclo-[6.3.0.0.4,110.5.9]undecanes
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The tandem 1,3-dipolar cycloaddition between sydnones and 1,5-cyclooctadiene provides 9,10-diazatetracyclo[6.3.0.0.4,110.5,9]undecanes (the Weintraub reaction) in modest to good yields.
- Gribble, Gordon W.,Hirth, Bradford H.
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p. 719 - 726
(2007/10/03)
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- Kinetic Studies on the Influence of Micellar Aggregates upon the Hydrolysis and Transnitrosation Reactions of N-methyl-N-nitrosotoluene-p-sulphonamide
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The basic hydrolysis of N-methyl-N-nitrosotoluene-p-sulphonamide and its transnitrosation reaction with secondary amines (sarcosine and dimethylamine) have been studied in the presence of cationic, anionic, and non-ionic micelles.The results show that the electric charge of the nucleophile is essential for the understanding of the micellar effects, which can be quantitatively rationalized on the basis of the pseudophase kinetic model.Thus the reaction with negatively charged nucleophiles is inhibited by both anionic and non-ionic surfactants, whereas cationic micelles increase the reaction rate, which passes through a maximum.The reaction between the substrate and a neutral nucleophile is, however, inhibited by all three classes of surfactant.
- Castro, Albino,Leis, J. Ramon,Pena, M. Elena
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p. 1221 - 1225
(2007/10/02)
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- Formation of Liquid-Crystal Phases in the Binary System Cetylpyridinium Bromide/N-Methylsydnone Studied by Light Microscopy and Small-Angle X-ray Diffraction
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Liquid-crystal phases were detected in the binary system cetylpyridinium bromide/N-methylsydnone by optical microscopy and small-angle X-ray diffraction.Surfactant self-aggregation can thus occur in aprotic solvents.Hydrogen bonding in solvents is thus not an essential requirement for molecular aggregation.
- Auvray, X.,Petipas, C.,Perche, T.,Anthore, R.,Marti, M.J.,et al.
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p. 8604 - 8607
(2007/10/02)
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- Nucleophilic Catalysis in the Nitrosation of Sarcosine and Proline
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The formation of nitrosoamino acids from both sarcosine (Sar) and proline (Pro) and nitrous acid is very strongly accelerated by thiourea (TU) and tetramethylthiourea (TMTU), and to a lesser extent by thiocyanate ion.The effects of TU and TMTU are very similar and are greater than that of SCN(1-) by a factor of 17 for Sar and 30 for Pro.Thus these amino acids behave like amines and not like amides (where there is no nucleophilic catalysis).The second-order rate constants (k2) for XNO attack were obtained (a) from the variation of the observed rate constant (k0) with or and (b) from the variation with .The agreement is excellent.This analysis assumes that reaction occurs as N-nitrosation of the free -NH- function.The variation of k0 with acidity, however, shows that there is another (small) component to the reaction, and the results are consistent with an earlier idea involving initial O-nitrosation at the -CO2(1-) function.The k2 values are discussed with reference to the reaction of other substrates with these (and other) nitrosating reagent, particularly with reference to encounter-controlled processes.The extent of the alternative pathway for ONSC(NH2)2(1+) decomposition is assessed in relation to the ability of this species to act as a nitrosating agent.
- Meyer, Thomas A.,Williams, D. Lyn H.
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p. 517 - 522
(2007/10/02)
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- Benzoyl phenyl 1-methylpyrazoles. Synthesis, characterization, and spectra
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The synthesis and unequivocal characterization of all six isomers of benzoyl phenyl 1-methylpyrazole (2) are described.The isomer of 2 isolated as one of the products of the reaction of 1,1-dimethyl-1-phenacylhydrazinium bromide (1) with base was shown to be only previously reported isomer, 5-benzoyl-3-phenyl-1-methylpyrazole (2b).
- Kano, Kunio,Scarpetti, David,Warner, John C.,Anselme, Jean-Pierre,Springer, James H.,Arison, Byron H.
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p. 2211 - 2219
(2007/10/02)
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- Nitrolysis of Tertiary Amines: Piperidines, Piperazines, Bisdimethylaminoalkanes, and Functionalized Methyldialkylamines
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Preparative amounts of mono- and di-nitrosamines were obtained from aliphatic cyclic and acyclic tertiary monamines and diamines by treatment with dinitrogen tetraoxide in carbon tetrachloride at 0 - 45 deg C.N-Methyl- and N-ethyl-piperidines (1) and (2) gave N-nitrosopiperidine (15), but N-isopropyl- and N-t-butyl-piperidines (3) and (4) did not.N-Methyl-, N-ethyl-, N-isopropyl- and N-t-butyl-N'-methylpiperazines (5) - (8) gave N,N'-dinitrosopiperazine (22) (in 90 percent, 81 percent, 55 percent, and 8 percent yields, respectively) and the diamine (8) also gave N-t-butyl-N'-dinitrosopiperazine (23) (45 percent).The N'-nitroso and the N'-nitro derivatives of N-methylpiperazine were similarly converted into N,N'-dinitroso- and N-nitroso-N'-nitropiperazines (22) (45 percent) and (30) (53 percent).Bisdimethylaminoalkanes (Me2N)2(CH2)n (10) - (14) gave bismethylnitrosaminoalkanes 2(CH2)n (24) - (27) and dimethylnitrosamine (28): n=1 (0 percent, 90 percent); n=2 (68 percent, 0 percent); n=3 (48 percent, 43 percent); n=4 (41 percent, 38 percent); n=6 (58 percent, 35 percent). β-Dimethylaminopropionitrile (18), 1-methylnitrosamino-2-dimethylaminoethane (17), and α-dimethylaminoacetic acid (19) gave the corresponding nitrosoamines by replacement of an N-methyl group.
- Boyer, Joseph H.,Kumar, Govindarajulu,Pillai, T. Perumal
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p. 1751 - 1754
(2007/10/02)
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- The mechanism of the nitrosation of α-amino acids: Evidence for an intramolecular Pathway
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The results of a kinetic study of the nitrosation of sarcosine, proline, cysteine, and the ethyl ester of sarcosine are reported.Under the conditions in which sarcosine and proline were studied, both first- and second-order terms were found for nitrite dependence.The experimental results are interpreted by a mechanism which involves NO(1+) and N2O3 as direct nitrosating agents, while the effect of acidity changes on the firts-oredr term for nitrite shows that the N-nitroso compound is also formed in a parallel reaction in which a slow intramolecular rearrangement follows the attack of NO(1+) on the carboxylate group of the amino acid.This pathway is confirmed by the absence of sucy a parallel reaction in the nitrosation of the ethyl ester of sarcosine.The influence of acidity on the nitrosation of cysteine shows that S-nitrosation is brought about by the reaction of NO(1+) with both the N-protonated, HSCH2-CH(NH3(1+))-COOH, and zwitterion, HSCH2-CH(NH3(1+))-COO(1-), forms of the amino acid.The values obtained for the bimolecular rate constants are compatible with diffusion control, the difference between the values for both forms of the amino acid explicable in terms of charges of the reagents.
- Casado, Julio,Castro, Albino,Leis, J. Ramon,Mosquera, Manuel,Pena, M. Elena
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p. 1859 - 1864
(2007/10/02)
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- Photochemistry of N-nitroso-N-alkyl amino acids: a facile oxidative decarboxylation
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Several N-alkyl or N-phenyl-N-nitroso α-amino acids were synthesized and were shown to photolytically rearrange to amidoximes with concurrent decarboxylation in solution or solid states without the presence of externally added acids.In contrast, N-nitrosonipecotinic acid, a N-nitroso β-amino acid, as well as N-nitrosopiperidine in the presence of acetic acid were not photolabile.The photolability of N-nitroso α-amino acids was ascribed to the presence of an intramolecular association between the nitrosamino and carboxyl groups through hydrogen bonding.The species having the hydrogen bonding through the nitroso oxygen in the Z-configuration was believed to be photolabile and decomposed to alkylideneimines as the primary product.The mechanism of the oxidative photorearrangement was discussed.
- Chow, Yuan L.,Horning, Douglas P.,Polo, Joel
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p. 2477 - 2483
(2007/10/02)
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