Quinoline Oximes: Synthesis,Reactions, and Biological Activity. (Review)

Data on the production and the reactions of quinoline aldoximes and ketoximes and their derivatives are reviewed. The synthesis of new heterocycles based on quinoline oximes is examined separately. The main results from investigation of the biological activity of quinoline oximes are presented.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 163–190, February, 2005.     

Furan and Thiophene Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of furan and thiophene aldoximes, ketoximes, and amidoximes and their reactions are reviewed. The synthesis of new heterocycles from furan and thiophene oximes and the biological activity of derivatives of the oximes are discussed individually.     

Pyridine Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of pyridine aldoximes, ketoximes, amidoximes, and their derivatives and their reactions are reviewed. The synthesis of new heterocycles from pyridine oximes is discussed separately. The principal results of research into the biological activity of the oximes are presented.     

Pyrrole Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on the production methods and reactions of pyrrole aldoximes and ketoximes and their derivatives are reviewed. The synthesis of new heterocycles from the pyrrole oximes is examined separately. The principal results from investigation of the biological activity of pyrrole oximes are described.     

Oximes of five-membered heterocyclic compounds with two heteroatoms 2. Reactions and biological activity (Review)

Data on the reactions of oxazole, thiazole, pyrazole, and imidazole aldoximes, ketoximes, amidoximes, and their derivatives are reviewed. The synthesis of new heterocycles based on the oximes of five-membered heterocyclic compounds with two heteroatoms are considered separately. The principal results from investigation of the biological activity of the ethers of these oximes are also presented. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1123–1155, August, 2007.     

Indole and Isatin Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of isatin and indole aldoximes, ketoximes, and amidoximes and their reactions are reviewed. Individual syntheses of new heterocycles from indole and isatin oximes are discussed. The principal results from investigation of the biological activity of derivatives of the oximes are also presented.     

Oximes of six-membered heterocyclic compounds with two and three heteroatoms. II.* Reactions and biological activity (review)

Data on the reactions of pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, and thiadiazine aldoximes, ketoximes, and amidoximes and their derivatives are reviewed. The synthesis of new heterocycles based on the oximes of six-membered heterocyclic compounds with two and three heteroatoms is considered separately. The principal results of research into the biological activity of these oximes and their ethers are also presented.     

Novel and efficient synthesis of N,N-dialkylamino-O-alkyl-2-(1-methyl-2-oxopropylidene)phosphorohydrazido oximes. Part 3

A novel and efficient method has been developed for the synthesis of N,N-dialkylamino-O-alkyl-2-(1-methyl-2-oxopropylidene)phosphorohydrazido oximes 5. The reactions involve the condensation of diacetylmonoxime and N,N-dialkylamino-O- alkylphosphorohydrazides in the presence of activated silica and give the corresponding target oximes in excellent yields under mild conditions.     

Efficient and divergent synthesis of fully substituted 1H-pyrazoles and isoxazoles from cyclopropyl oximes

Efficient and divergent one-pot synthesis of fully substituted 1H-pyrazoles and isoxazoles from cyclopropyl oximes based on reaction conditions selection is reported. Under Vilsmeier conditions (POCl3/DMF), substituted 1 H-pyrazoles were synthesized from 1-carbamoyl, 1-oximyl cyclopropanes via sequential ring-opening, chlorovinylation, and intramolecular aza-cyclization. In the presence of POCl3/CH2Cl2, substituted isoxazoles were obtained from the cyclopropyl oximes via ring-opening and intramolecular nucleophilic vinylic substitution (SNV) reactions.     

肟的无气味硫缩醛/酮化反应

探讨了以无气味且稳定的α-羰基二硫缩烯酮(1)作为代硫醇试剂的肟(2)的硫缩醛/酮化反应. 在乙酰氯-乙醇(体积分数95%)或4-十二烷基苯磺酸(DBSA)-水体系中及回流条件下, 化合物1与肟2能有效地进行硫缩醛/酮化反应. 反应过程中未闻到硫醇的恶臭气味.     

Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines,Quinolines, and Phenanthridines

A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)₃] as a photoredox catalyst, the acyl oximes were converted by 1 e^? reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids.     

Visible‐Light‐Promoted Iminyl‐Radical Formation from Acyl Oximes: A Unified Approach to Pyridines,Quinolines, and Phenanthridines

A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac‐[Ir(ppy)₃] as a photoredox catalyst, the acyl oximes were converted by 1 e⁻ reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N‐containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible‐light‐induced iminyl‐radical formation was successfully applied to a five‐step concise synthesis of benzo[c]phenanthridine alkaloids.     

Mechanism of stable radical generation in aromatic polyamides on exposure to nitrogen dioxide

By using the example of poly-m-phenylene isophthalamide, the mechanism of generation of stable nitrogen-containing radicals in aromatic polyamides in the presence of nitrogen dioxide is considered. The proposed mechanism is based on the reactions of dimers of nitrogen dioxide in the form of nitrosyl nitrate. As a result of a primary reaction of electron transfer from donor functional groups of macromolecules to nitrosyl nitrate, macromolecular radical cations and nitric oxide are formed. Amide groups and phenyl rings can act as electron donors. In the subsequent reactions with participation of radical cations, nitric oxide and nitrogen dioxide oximes, nitroso compounds and nitrites are formed. Generation of stable iminoxyl radicals occurs by reactions of oximes with nitrogen dioxide. Thermolysis of the polymer nitration products gives iminoxyl and acylarylaminoxyl radicals. The structure of iminoxyl radicals and features of dynamics of their formation have been confirmed by ab initio quantum-chemical calculations.     

Cp*CoIII Catalyzed Site‐Selective CH Activation of Unsymmetrical O‐Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes

The synthesis of isoquinolines by site‐selective C? H activation of O‐acyl oximes with a Cp*Co^III catalyst is described. In the presence of this catalyst, the C? H activation of various unsymmetrically substituted O‐acyl oximes selectively occurred at the sterically less hindered site, and reactions with terminal as well as internal alkynes afforded the corresponding products in up to 98 % yield. Whereas the reactions catalyzed by the Cp*Co^III system proceeded with high site selectivity (15:1 to 20:1), use of the corresponding Cp*Rh^III catalysts led to low selectivities and/or yields when unsymmetrical O‐acyl oximes and terminal alkynes were used. Deuterium labeling studies indicate a clear difference in the site selectivity of the C? H activation step under Cp*Co^III and Cp*Rh^III catalysis.     

Transformations of sym-octahydroxanthene-1,8-diones and 1,8-dioxo-sym-octahydroxanthylium salts in recyclization under the influence of amines

The chemical behavior of 9-R-sym-octahydroxanthene-1,8-diones and salts based on them in recyclization reactions under the influence of amines was studied. The effect of the basicity of the amines on the direction of recyclization was established. A method is proposed for the single-stage synthesis of sym-octahydroacridine-1.8-dione oximes based on 1,8-dioxo-sym-octahydroxanthenes. Conditions were worked out for the oxidation of sym-octahydroxanthene-1,8-diones and N-R-decahydroacridinediones to the corresponding salts. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–38, January, 2006.     

Synthesis of azaheterocycles from aryl ketone O-acetyl oximes and internal alkynes by Cu-Rh bimetallic relay catalysts

A synthetic method for azaheterocycles from aryl ketone O-acetyl oximes and internal alkynes has been developed by using the Cu(OAc)(2)-[Cp*RhCl(2)](2) bimetallic catalytic system. The reactions proceeded with both of anti- and syn-isomers of oximes with a wide scope of substituents. The Cu-Rh bimetallic system could be applied for the synthesis of isoquinolines as well as β-carboline, furo[2.3-c]pyridine, pyrrolo[2,3-c]pyridine, and thieno[2,3-c]pyridine derivatives.     

The chemistry ofN,N-bis (trialkylsilyloxy) enamines

The reactions of primary amines withN,N-bis(trimethylsilyloxy) enamines can give products of both mono-and bis-α-oximinoalkylation of primary amines. The steric restrictions in both reactants substantially retard bis-α-oximinoalkylation. A general method for the synthesis of α-amino-substituted oximes from primary amines and bis-silyl derivatives of aliphatic nitro compounds was developed. For Part 1, see Ref. 1. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1265–1272, July, 2000.     

Advances in the field of the synthesis of amino derivatives of terpenoids

Information on the synthesis of amino derivatives of monoterpenes by the reduction of oximes by the Leuckart reaction, and by the reductive amination of ketones by amines and nitriles is generalized. The stereochemistry of the amines formed as the result of the above-mentioned reactions is discussed.Institute of Physical Organic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 145–159, March–April, 1982.     

Studies in pyran,its analogs,and related compounds

The lithium aluminum hydride reduction of the ethers and tosylates of chroman-4-one oxime and related compounds has been studied. It has been found that the ethers of the oximes, like the oximes, do not undergo a normal, but rather an anomalous, reduction. The tosylates of the oximes exhibit a higher tendency to undergo anomalous reduction than the corresponding oximes. During the synthesis of the ethers of the oximes it was established that the use of dimethylformamide as the medium for alkylation of the oxime salts helps to suppress the side reaction forming nitrones.For part XXXVII, see [23].     

Pentafluorophenyl complexes of cobalt(III) with 1-(diacetylmonoximatoimino)-3-(diacetylmonoximeimino)-propane (dotnH)

Cyclopalladation of vinylic oximes occurs for the sterically rigid oximes of 1-benzalcyclohexanone and 1-acetylcyclohexene giving dimeric complexes which retain the alkene double bond. The presence of the vinylic palladium bond is shown both by spectroscopic methods and cleavage reactions using carbon monoxide or cyanide ion. The complexes do not make good substrates for the synthesis of vinylic oxime derivatives.