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1.
B. I. Khristich V. A. Kruchinin A. F. Pozharskii A. M. Simonov 《Chemistry of Heterocyclic Compounds》1971,7(6):759-762
The quinoline ring in imidazo[4,5-f]quinolines is more reactive than the imidazole ring with respect to nucleophiles (phenyllithium and sodium amide). An assumption, which is confirmed by molecular orbital calculations and the pKa values, is expressed that the direction of the corresponding reactions is primarily determined by the relative basicity of the aza groups (the nucleophile attacks the C atom next to the more basic nitrogen atom) and not by the magnitude of the positive charge or the energy of anionic localization on the C2 and C7 atoms in the neutral molecule.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 814–817, June, 1971. 相似文献
2.
Ertürk H Maigut J Puchta R van Eldik R 《Dalton transactions (Cambridge, England : 2003)》2008,(20):2759-2766
Complexes of the type [Pt2(N,N,N',N'-tetrakis(2-pyridylmethyl)diamine(HO)2]4+ and [Pt2(N,N,N',N'-tetrakis(2-pyridylmethyl)diamine(Cl)2]2+ were used to study their reactions with a series of bio-relevant nucleophiles, viz. thiourea, L-methionine and guanosine-5'-monophosphate (5'-GMP2-) as a function of nucleophile concentration and temperature. The reactions with the sulfur containing nucleophiles (thiourea and L-methionine) were followed under pseudo-first-order conditions by stopped-flow and UV-Vis spectrophotometry. The reaction with 5'-GMP2- was carried out under second order conditions and studied by NMR spectroscopy. The results indicate that the bridged dinuclear complexes remain intact after coordination of the studied nucleophiles for an extended period of time, which differs significantly from that reported for other multinuclear platinum complexes in the literature. 相似文献
3.
A dinuclear platinum(II) complex that was recently investigated in our group was tested for its cytostatic activity and found to be active against HeLa S3 cells. The complex consists of a bidentate N,N-donor chelating ligand system in which the two platinum centers are connected by an aliphatic chain of 10 methylene groups. The complex [Pt(2)(N(1),N(10)-bis(2-pyridylmethyl)-1,10-decanediamine)(OH(2))(4)](4+) (10NNpy) is of further special interest, since only little is known about the substitution behavior of such dinuclear platinum complexes that contain a bidentate coordination sphere. The complex was investigated using different biologically relevant nucleophiles, such as thiourea (tu), L-methionine (L-Met), glutathione (GSH), and guanine-5'-monophosphate (5'-GMP), at two different pH values (2 and 7.4). The substitution of coordinated water by these nucleophiles was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV-vis spectroscopy. The reactivity of 10NNpy with the selected nucleophiles was found to be tu ? 5'-GMP > L-Met > GSH at pH 2 and GSH > tu > L-Met at pH 7.4. The results for the dinuclear 10NNpy complex were compared to those for the corresponding mononuclear reference complex [Pt(aminomethylpyridine)(OH(2))(2)](2+), Pt(amp), studied before in our group, by which the effect of the addition of an aliphatic chain, an increase in the overall charge, and a shift in the pK(a) values of the coordinated water ligands could be investigated. The reactivity order for Pt(amp) was found to be tu > GSH > L-Met at pH 7.4. 相似文献
4.
Djuran Miloš I. Dimitrijević Dejana P. Milinković Snežana U. Bugarčić Živadin D. 《Transition Metal Chemistry》2002,27(2):155-158
The reactions between two monofunctional platinum complexes [Pt(Me4dien)Cl]+ (Me4dien = 1,1,7,7-tetramethyl-diethylenetriamine) and [Pt(Et4dien)Cl]+ (Et4dien = 1,1,7,7-tetraethyldiethylenetriamine) and the peptides, N-acetylated L-methionyl-L-histidine (MeCO–Met–His) and glutathione (GSH), have been investigated by 1H-n.m.r. spectroscopy and u.v.–vis. spectrophotometry. The reactions of the platinum(II) complexes with MeCO–Met–His were carried out at room temperature and at pH 3.0 and 7.0, whereas with GSH the reactions were studied only at pH 3.0. No binding of these two platinum complexes to the sulfur atom of methionine or to nitrogen atoms of histidine residue of MeCO–Met–His was observed during the first 24 h. When the reaction was followed further, after 24 h very slow binding of [Pt(Me4dien)Cl]+ to the N3 nitrogen atom of imidazole was observed. Both platinum complexes react with the sulfur atom of the cysteine residue in GSH. Kinetic data show that GSH reacts twice as fast with [Pt(Me4dien)Cl]+ than with [Pt(Et4dien)Cl]+. Our findings indicate that sterically crowded platinum(II) complexes are only capable of reacting with the sulfhydryl group of the cysteine residue. This influences the design of new platinum(II) complexes for selective covalent modification of peptides and proteins. 相似文献
5.
o-Quinone methides are formed from the reaction of nucleophiles with trimethylsilyl(methyl)-1,4-benzoquinones. These reactive intermediates are trapped by excess nucleophile to form substituted quinones following oxidation. In addition, varying amounts of a symmetrical dimer and a xanthen derivative were observed. The influence of different nucleophiles and ring substituents on the rate of reaction have been studied, and are consistent with rate-limiting formation of a vinylogous enolate initiated by attack of the nucleophile on the silyl group. 相似文献
6.
Access to Optically Active 3‐Substituted Piperidines by Ring Expansion of Prolinols and Derivatives
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Dr. Domingo Gomez Pardo Prof. Janine Cossy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4516-4525
The ring expansion of prolinols via an aziridinium intermediate gives C3‐substituted piperidines in good yields and enantiomeric excess, the substituent at the C3 position being derived from the most reactive nucleophile in the reaction mixture. Depending on the nucleophile, the reaction proceeds under thermodynamic or kinetic control. The regioselectivity of attack of nucleophiles on the aziridinium intermediate depends on the nature of the substituents on the nitrogen atom and the C4 position of the starting prolinols. 相似文献
7.
Miyabe H Yoshida K Reddy VK Matsumura A Takemoto Y 《The Journal of organic chemistry》2005,70(14):5630-5635
[reaction: see text] The viability of oximes as nucleophiles in transition-metal-catalyzed allylic substitution was examined. The oxygen atom of oxime acted as a reactive nucleophile in the reaction of a pi-allyl palladium complex. In the presence of Pd(PPh3)4, the allylic substitution of oximes with allylic carbonate afforded the linear O-allylated oxime ethers selectively without a base. In contrast, the palladium-catalyzed reaction with allylic acetate proceeded smoothly in the presence of K2CO3 or Et2Zn as a base. Selective formation of nitrones was achieved by using palladium(II) catalyst. In the presence of Pd(cod)Cl2, the allylic substitution of oximes with allylic acetate afforded the N-allylated nitrones under solvent-free conditions, as a result of the reaction with the nitrogen atom of oximes. 相似文献
8.
Quinazoline isothiocyanate 1 reacts with various nucleophiles(nitrogen nucleophiles,oxygen nucleophiles and sulphur nucleophiles)to afford heterocyclic systemes 2-13,Also,the [4 2] cycloaddition reaction of 1 with phenyl isocyanate,benzylidene aryl amine and cinnamic acid derivatives gave novel heterocyclic compounds 14-16,Moreover,the reaction of 1 with active methylene compounds under Michael reaction conditions also was investigated to yield 17 and 18 and it was found that all these reactions proceede via isothiocyanate heterocyclization to furnish non-condensed heterocyclic compoundes,Some of the newly synthesized compounds were tested for their antimicrobial activities. 相似文献
9.
Huffman LM Casitas A Font M Canta M Costas M Ribas X Stahl SS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(38):10643-10650
A well-defined macrocyclic aryl–Cu(III) complex (2) reacts readily with a variety of oxygen nucleophiles, including carboxylic acids, phenols and alcohols, under mild conditions to form the corresponding aryl esters, biaryl ethers and alkyl aryl ethers. The relationship between these reactions and catalytic C-O coupling methods is demonstrated by the reaction of the macrocyclic aryl–Br species with acetic acid and p-fluorophenol in the presence of 10 mol% Cu(I). An aryl-Cu(III)-Br species 2(Br) was observed as an intermediate in the catalytic reaction. Investigation of the stoichiometric C-O bond-forming reactions revealed nucleophile-dependent changes in the mechanism. The reaction of 2 with carboxylic acids revealed a positive correlation between the log(k(obs)) and the pK(a) of the nucleophile (less-acidic nucleophiles react more rapidly), whereas a negative correlation was observed with most phenols (more-acidic phenols react more rapidly). The latter trend resembles previous observations with nitrogen nucleophiles. With carboxylic acids and acidic phenols, UV-visible spectroscopic data support the formation of a ground-state adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl-O coupling from the Cu(III) complex, consisting of nucleophile coordination to the Cu(III) center, deprotonation of the coordinated nucleophile, and C-O (or C-N) reductive elimination from Cu(III). 相似文献
10.
Prof. Dr. Pavel Kočovský Prof. Dr. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):36-56
In this review the stereochemistry of palladium‐catalyzed addition of nucleophiles to alkenes is discussed, and examples of these reactions in organic synthesis are given. Most of the reactions discussed involve oxygen and nitrogen nucleophiles; the Wacker oxidation of ethylene has been reviewed in detail. An anti‐hydroxypalladation in the Wacker oxidation has strong support from both experimental and computational studies. From the reviewed material it is clear that anti‐addition of oxygen and nitrogen nucleophiles is strongly favored in intermolecular addition to olefin–palladium complexes even if the nucleophile is coordinated to the metal. On the other hand, syn‐addition is common in the case of intramolecular oxy‐ and amidopalladation as a result of the initial coordination of the internal nucleophile to the metal. 相似文献
11.
S. V. Makarov E. V. Kudrik I. N. Terskaya K. A. Davydov 《Russian Journal of General Chemistry》2004,74(9):1383-1385
The reaction mechanism of thiourea dioxides with ammonia and primary aliphatic amines involves direct nucleophile (ammonia or amine) reactions with thiourea dioxides, followed by dissociation of the resulting adduct to form the sulfoxylate ion.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1491–1494.Original Russian Text Copyright © 2004 by Makarov, Kudrik, Terskaya, Davydov.This revised version was published online in April 2005 with a corrected cover date. 相似文献
12.
The Tsuji-Trost Reaction is a palladium-catalysed allylation of nucleophiles that consists in the reaction of a nitrogen, carbon or oxygen-based nucleophiles with an allylic substrate bearing a leaving group. Here we present the use of 2-nitrosulfonamide derivatives as nucleophile, which are reactive under mild conditions. 2-nitrosulfonyl groups are well-known dual protective activator groups easy to introduce in any type of amine substrates. The resulting 2-nitrosulfonamide derivatives are ideal substrates for the Tsuji-Trost reaction to afford a convenient and flexible access to primary and dissymmetric secondary allyl amines. The optimised procedure is flexible (for solvent, temperature, functional groups) and has been applied with good to excellent yield to access to a wide range of allyl amine derivatives. 相似文献
13.
S. G. Pukhovskaya L. Zh. Guseva S. V. Makarov E. V. Naidenko 《Journal of Analytical Chemistry》2005,60(1):21-23
A new simple and reliable procedure was developed for the spectrophotometric determination of nitrogen(II) oxide. The procedure is based on the determination of excess oxygen after its reaction with NO. Alkaline solutions of thiourea dioxide were used for the determination of oxygen. It was found that the decomposition of an alkaline solution of thiourea dioxide under aerobic conditions is accompanied by the formation of dithionite, and its concentration is proportional to the concentration of oxygen in the solution. The absorbance of the resulting dithionite was measured at 315 nm. The solutions obeyed Beers law at oxygen concentrations of 1 × 10–5–1.5 × 10–3 M. The analytical range for NO was 1 × 10–5–1.5 × 10–3 M. The proposed procedure was also used for the determination of nitrogen(II) oxide in aqueous-ethanolic solutions.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 1, 2005, pp. 27–29.Original Russian Text Copyright © 2005 by Pukhovskaya, Guseva, Makarov, Naidenko. 相似文献
14.
15.
Conclusions The reaction of cationic allyl complexes of manganese, rhodium, and iron with organometallic nucleophiles may proceed by three pathways: 1) addition of the nucleophile, 2) transallylation, and 3) reduction of the cationic complex.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2606–2609, November, 1987. 相似文献
16.
Reza Ranjbar-Karimi Roghayeh Danesteh Khalil Beiki-Shoraki 《Arabian Journal of Chemistry》2019,12(8):2037-2043
In this study, the reaction of pentafluoropyridine and 4-phenylsulfonyl tetrafluoropyridine with difunctional nitrogen and sulfur nucleophiles such as thiourea, thioamide derivatives, and unsymmetrical bidentate nitrogen nucleophiles such as diamino-triazole and amino-imidazole in the presence of sodium carbonate was investigated. 相似文献
17.
Bali MS Buck DP Coe AJ Day AI Collins JG 《Dalton transactions (Cambridge, England : 2003)》2006,(45):5337-5344
The effect of encapsulation by cucurbiturils Q[7] and Q[8] on the rate of reaction of the anti-cancer dinuclear platinum complex trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ with the model biological nucleophiles glutathione and cysteine has been examined by NMR spectroscopy. It was expected that the octamethylene linking chain would fold inside the cucurbituril host and hence position the reactive platinum centres close to the cucurbituril portals, and thereby, confer resistance to degradation by biological nucleophiles. The upfield shifts of the resonances from the methylene protons in the linking ligand observed in 1H NMR spectra of the platinum complex upon addition of either Q[7] or Q[8] indicate that the cucurbituril is positioned over the linking ligand, with the Pt(II) centres projecting out of the portal. Furthermore, the relative changes in chemical shift of the methylene resonances suggest that the octamethylene linking chain folds within the cucurbituril cavity, particularly in Q[8]. Simple molecular models, based on the observed relative changes in chemical shift, could be constructed that were consistent with the proposed folding of the linking ligand within the cucurbituril cavity. Encapsulation by Q[7] was found to reduce the rate of reaction of the platinum complex with glutathione. Encapsulation by Q[7] and Q[8] was also found to reduce the rate of reaction of the platinum complex with cysteine, with Q[8] slowing the reaction to a greater extent than Q[7], consistent with the inferred encapsulation geometries. Encapsulation of dinuclear platinum complexes within the cucurbituril cavity may provide a novel way of reducing the reactivity and degradation of these promising chemotherapeutic agents with blood plasma proteins. 相似文献
18.
Alexis D.C. Parenty 《Tetrahedron》2005,61(35):8410-8418
Secondary amines and thiols undertake a substitution reaction on the side chain of 2-bromoethyl-pyridinium derivatives ‘directed’ by an intramolecular re-arrangement. Experimental investigations strongly indicate that the reaction is initiated by an alpha addition of the nucleophile onto the iminium moiety of the N-heteroaromatic cation, followed by a cyclisation and an oxidative ring opening. This novel substitution process is able to occur with less reactive nucleophiles that would not undergo conventional substitution with ‘isolated’ bromoethyl moieties. 相似文献
19.
Kissane M Murphy M O'Brien E Chopra J Murphy L Collins SG Lawrence SE Maguire AR 《Organic & biomolecular chemistry》2011,9(7):2452-2472
Synthetically versatile conjugate addition of a range of carbon, nitrogen, oxygen, sulfur and selenium nucleophiles to the highly functionalised 2-thio-3-chloroacrylamides is described. The stereochemical and synthetic features of this transformation are discussed in detail. In most instances, the nucleophile replaces the chloro substituent with retention of stereochemistry. With the oxygen nucleophiles, a second addition can occur leading to acetals, while with the nitrogen nucleophiles, E-Z isomerism occurs in the resulting enamine derivatives. The ratio of the E/Z isomers can be rationalised on the basis of the substituent and the level of oxidation. 相似文献
20.
[reaction: see text] The viability of hydroxylamines as nucleophiles in transition-metal-catalyzed allylic substitutions was examined. We have found that the oxygen atom of hydroxylamines having an N-electron-withdrawing substituent (also known as hydroxamic acids) acts as a reactive nucleophile. The palladium-catalyzed O-allylic substitution of hydroxylamines with allylic carbonate afforded the linear hydroxylamines. The selective formation of the branched hydroxylamines was observed in iridium-catalyzed reaction. Regio- and enantioselective allylic substitution of the unsymmetrical phosphates with hydroxylamines was studied by using the iridium complex of chiral pybox ligand. The aqueous-medium reaction with hydroxylamines proceeded smoothly in the presence of Ba(OH)(2).H(2)O to give the branched products with good enantioselectivities. 相似文献