The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were us...The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were used to build 3D-QSAR models for a series of N-benzyl isatin oximes JNK inhibitors. The best models were obtained for the receptor-based alignment with CoMSIA combining steric （S）, electrostatic （E）, and hydrogen bond donor （D） and hydrogen bond acceptor （A） fields （q2 = 0.759, r2 = 0.966, r2 pred = 0.703）. Based on the contour maps of RB CoMSIA model, some key structural factors responsible for inhibitory activity were investigated. Large groups at N-substituent or R6 position are preferred to interact with hydrophobic residues Ile70, Asp150, Ala151, Asn152 and Ser193. Electron-donating or hydrogen bond donor groups on the isatin ring would form polar and hydrogen bond with the negative-charged residue Glu147. In addition, electron-withdrawing groups or hydrogen bond acceptor group near the N-substituent would enhance inhibitory activity. The results are in good accordance and complementary to each other. The developed models could provide guidance in the rational design of more potent and selective JNK inhibitors.展开更多
Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Re...Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Recent advances for the synthesis of nitriles through photoinduced C—C bond cleavage of cycloketone oximes classified by the type of C—X bond forming are summarized.Various compounds possessing nitriles can be efficiently accessed via this method.展开更多
Dioxane-NO2 was employed to oxidize oximes to corresponding aldehydes and ketones in high yield in nonaqueous condition at room temperature. Thr reaction proved to be mild and selective.
The Beckmann rearrangement of cyclohexanone oxime was achieved by the combined use of cobalt salt and Lewis acids co-catalysts (each 10 mol%). Various combinations of cobalt salts and Lewis acids gave lactams in a sat...The Beckmann rearrangement of cyclohexanone oxime was achieved by the combined use of cobalt salt and Lewis acids co-catalysts (each 10 mol%). Various combinations of cobalt salts and Lewis acids gave lactams in a satisfactory yield under mild conditions. This method makes it possible to reduce undesirable byproducts.展开更多
A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al（NO3）3·9H2O in presence of catalytic amounts of NaBr in CH2Cl2 at room temperature.
A variety of carbonyl compounds can be converted into oximes efficiently and conveniently in a novel ionic liquid/water bi-phasic system in the presence of sodium bicarbonate at ambient temperature. The ionic liquid 1...A variety of carbonyl compounds can be converted into oximes efficiently and conveniently in a novel ionic liquid/water bi-phasic system in the presence of sodium bicarbonate at ambient temperature. The ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate [bmim]PF6 is immiscible with water or diethyl ether and can be easily recycled for reuse without noticeable droping in activity after separation of the products. The protocol is rapid, the yields are excellent, the method is simple and the ionic liquid can be reused.展开更多
Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room...Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room temperature. Excellent conversion and selectivity were acquired in the Beckmann rearrangement of cyclohexanone oxime. The catalyst system was recycled and reused.展开更多
Among sensitizing systems, the combination of benzophenone(BP) and tertiary amines(TA) has been deeply studied. Since the structure of O-acyl-oximes is similar to that of BP and their triplet state energies are nearly...Among sensitizing systems, the combination of benzophenone(BP) and tertiary amines(TA) has been deeply studied. Since the structure of O-acyl-oximes is similar to that of BP and their triplet state energies are nearly equal, we want to know whether the behavior of the photopolymerization initiated with O-acyl-oximes—TA system is the same as that of photopolymerization initiated with展开更多
Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amoun...Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.展开更多
A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that ...A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.展开更多
A convenient synthesis of 1-alkyl-2-chloro-1H-indole-3-carbaldehyde oximes（5a―5d） and 1-alkyl-2-phenoxy-1H-indole-3-carbaldehyde oximes（6a―6d） from 2-indolone was completed via the Vilsmeier-Haack reac-tion,with...A convenient synthesis of 1-alkyl-2-chloro-1H-indole-3-carbaldehyde oximes（5a―5d） and 1-alkyl-2-phenoxy-1H-indole-3-carbaldehyde oximes（6a―6d） from 2-indolone was completed via the Vilsmeier-Haack reac-tion,with N-alkylation and oximation as the key steps.An improved one-pot method for the synthesis of 1-alkyl-2-alkoxy-1H-indole-3-carbaldehyde oximes（7a―7h） from 1-alkyl-2-chloro-1H-indole-3-carbaldehydes（3a―3d） was described.The Williamson reactions and esterification reactions were performed and the oxime-ethers and oxime-esters were synthesized,respectively.The new synthesized compounds（3a―11d） were characterized by 1H NMR,IR,MS,and elemental analysis.展开更多
O-Alkylation of oximes with N-vinylpyrrolidin-2-one or N-methyl-N-vinylacetamide was efficiently initiated by a catalytic amount of cerium（Ⅳ） ammonium nitrate（CAN）,giving the corresponding oxime ether derivatives...O-Alkylation of oximes with N-vinylpyrrolidin-2-one or N-methyl-N-vinylacetamide was efficiently initiated by a catalytic amount of cerium（Ⅳ） ammonium nitrate（CAN）,giving the corresponding oxime ether derivatives in good yield.展开更多
A novel photoredox-neutral ring-opening pyridylation of non-prefunctionalized cyclic oximes has been accomplished through phosphoranyl radical-mediated N-O/C-C bond cleavages followed by radicalradical coupling.This m...A novel photoredox-neutral ring-opening pyridylation of non-prefunctionalized cyclic oximes has been accomplished through phosphoranyl radical-mediated N-O/C-C bond cleavages followed by radicalradical coupling.This mild acid-,base-,and oxidant-free protocol provides highly site-selective and efficient access to distally pyridylated alkylnitriles,which could be scale-up synthesized and readily converted into skeletally diverse compounds.Notably,the oxidized ground-state photocatalyst generated via the SET oxidation of the highly reducing excited-state photocatalyst by cyanopyridines might initiate the following phosphoranyl radical-mediated deoxygenative process.展开更多
A series of novel flavone-4-oximes[1]were synthesized by the oximation of substituted flavones.The synthesized compounds were characterized by various spectroscopic methods including IR,MASS,NMR spectroscopy.Out of th...A series of novel flavone-4-oximes[1]were synthesized by the oximation of substituted flavones.The synthesized compounds were characterized by various spectroscopic methods including IR,MASS,NMR spectroscopy.Out of the 14 test compounds screened for their antioxidant activity,compounds such as JGS-VI(a N,N dimethyl benzaldehyde derivative)and JGSVII(a 3,4 dimethoxy benzaldehyde derivative)exhibited antioxidant activity comparable to that of ascorbic acid with its IC50 value at 30.01 Mm as standard following DPPH?method.Compounds such as JGS-II(a Para fluro benzaldehyde derivative),JGS-IV(a Para methyl benzaldehyde derivative)and JGS-V(a thiophene-2-aldehyde derivative)exhibited anti-oxidant activity among all the test compounds screened against ABTS[2]using Quercetin with its IC50 value at 50.24 Mm.展开更多
A series of rotenone O-alkyl oxime derivatives was designed and synthesized. Their structures were confirmed by elemental analyses, Fourier transform infrared（FTIR） and 1H NMR spectral studies, and the typical cryst...A series of rotenone O-alkyl oxime derivatives was designed and synthesized. Their structures were confirmed by elemental analyses, Fourier transform infrared（FTIR） and 1H NMR spectral studies, and the typical crystal structure of rotenone O-ethyl oxime（3b） was determined by X-ray diffraction. The preliminary biological activities of the new compounds were evaluated. The results of bioassays indicate that the title compounds exhibit moderate insecticidal and bactericidal activities. Among the synthesized compounds, compound 3q exhibited 90.0% mortality against M. separata at 1000 μg/mL. Compounds 3b and 3g exhibited both 90.0% inhibition rate against R. solani at 500 μg/mL, respectively.展开更多
InCl3 catalyzes the reaction of hydroxylamine hydrochloride with a number of aldehydes and ketones under solvent free condition to afford an efficient method for the synthesis of oximes.*
Oximes derivatives have been vastly used in organic synthesis.In this review,C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed.According to th...Oximes derivatives have been vastly used in organic synthesis.In this review,C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed.According to the different type of products,this review was divided into three parts:(1)C(sp^(3))-H bond functionalization for C-C bond formation.(2)C(sp^(3))-H bond functionalization for C-N bond formation.(3)C(sp^(3))-H bond functionalization for C-S,C-F bond formation.展开更多
A convenient copper-catalyzed approach has been developed for the synthesis of substituted spiro-fused pyrazolin-5-ones from readily available cyclopropyl O-acyl ketoximes via an intramolecular N-N bond formation reac...A convenient copper-catalyzed approach has been developed for the synthesis of substituted spiro-fused pyrazolin-5-ones from readily available cyclopropyl O-acyl ketoximes via an intramolecular N-N bond formation reaction. These catalytic reactions proceed in excellent yields with a broad scope.展开更多
A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also ef...A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also efficient for the preparation of primary thiobenzamide from benzaldoxime. This approach features simple-operation, easy-control and good to excellent yields.展开更多
基金supported by the Beijing Natural Science Foundation(Grant No.2123062)Research Fund for the Doctoral Program of Higher Education of China(Grant No.20121103120008)Science and Tech-nology Foundation of Beijing University of Technology(Grant No.ykj-2012-8725)
文摘The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were used to build 3D-QSAR models for a series of N-benzyl isatin oximes JNK inhibitors. The best models were obtained for the receptor-based alignment with CoMSIA combining steric （S）, electrostatic （E）, and hydrogen bond donor （D） and hydrogen bond acceptor （A） fields （q2 = 0.759, r2 = 0.966, r2 pred = 0.703）. Based on the contour maps of RB CoMSIA model, some key structural factors responsible for inhibitory activity were investigated. Large groups at N-substituent or R6 position are preferred to interact with hydrophobic residues Ile70, Asp150, Ala151, Asn152 and Ser193. Electron-donating or hydrogen bond donor groups on the isatin ring would form polar and hydrogen bond with the negative-charged residue Glu147. In addition, electron-withdrawing groups or hydrogen bond acceptor group near the N-substituent would enhance inhibitory activity. The results are in good accordance and complementary to each other. The developed models could provide guidance in the rational design of more potent and selective JNK inhibitors.
基金support from the Natural Science Foundation of Gansu Province(No.3ZS061-A25-019)the Scientific Research fund of Gansu Provincial Education Department(No.0601-25)
文摘Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
基金the National Natural Science Foundation of China(Nos.21672037 and 21532001)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01005)。
文摘Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Recent advances for the synthesis of nitriles through photoinduced C—C bond cleavage of cycloketone oximes classified by the type of C—X bond forming are summarized.Various compounds possessing nitriles can be efficiently accessed via this method.
基金the National Natural Science Foundation of China and Henan Province Education Committee.
文摘Dioxane-NO2 was employed to oxidize oximes to corresponding aldehydes and ketones in high yield in nonaqueous condition at room temperature. Thr reaction proved to be mild and selective.
文摘The Beckmann rearrangement of cyclohexanone oxime was achieved by the combined use of cobalt salt and Lewis acids co-catalysts (each 10 mol%). Various combinations of cobalt salts and Lewis acids gave lactams in a satisfactory yield under mild conditions. This method makes it possible to reduce undesirable byproducts.
基金support for this work by the research facilities of Ilam University
文摘A wide variety of aldoximes and ketoximes were regenerated to corresponding carbonyl compounds with Al（NO3）3·9H2O in presence of catalytic amounts of NaBr in CH2Cl2 at room temperature.
基金The project was supported by the National Natural Science Foundation of China(No 20272018)the Guangdong Natural Science Foundation(No 021166,04010458)the Scientific Research Foundation for the Retumed Overseas Chinese Scholars,State Education Ministry of China.
文摘A variety of carbonyl compounds can be converted into oximes efficiently and conveniently in a novel ionic liquid/water bi-phasic system in the presence of sodium bicarbonate at ambient temperature. The ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphate [bmim]PF6 is immiscible with water or diethyl ether and can be easily recycled for reuse without noticeable droping in activity after separation of the products. The protocol is rapid, the yields are excellent, the method is simple and the ionic liquid can be reused.
文摘Silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via covalent bond has been proved to be green catalyst for liquid-phase Beckmann rearrangement of oximes in dried dioxane at room temperature. Excellent conversion and selectivity were acquired in the Beckmann rearrangement of cyclohexanone oxime. The catalyst system was recycled and reused.
文摘Among sensitizing systems, the combination of benzophenone(BP) and tertiary amines(TA) has been deeply studied. Since the structure of O-acyl-oximes is similar to that of BP and their triplet state energies are nearly equal, we want to know whether the behavior of the photopolymerization initiated with O-acyl-oximes—TA system is the same as that of photopolymerization initiated with
文摘Beckmann rearrangements of oximes to lactams often require harsh conditions and/or the use of large amounts of acid catalyst. To reduce the amount of Bronsted acid required, and to avoid the formation of a large amount of undesirable byproducts under mild reaction conditions, a low environmental load process was developed. Beckmann rearrangements of cyclohexanone oxime and cyclooctanone oxime were achieved using a combination of a Bronsted acid and cobalt tetra-fluoroborate hexahydrate. Various Bronsted acid catalysts (10 - 20 mol%) were used to obtain the corresponding lactams in high yields at 80℃.
基金financial supported by the National Natural Science Foundation of China(No.21202089)China Postdoctoral Science Foundation(No.2013M531145)the Research Foundation of the Six People Peak of Jiangsu Province(No.2013-SWYY-013)
文摘A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.
基金Supported by the Natural Science Foundation of Liaoning Province,China(No.202142037)
文摘A convenient synthesis of 1-alkyl-2-chloro-1H-indole-3-carbaldehyde oximes（5a―5d） and 1-alkyl-2-phenoxy-1H-indole-3-carbaldehyde oximes（6a―6d） from 2-indolone was completed via the Vilsmeier-Haack reac-tion,with N-alkylation and oximation as the key steps.An improved one-pot method for the synthesis of 1-alkyl-2-alkoxy-1H-indole-3-carbaldehyde oximes（7a―7h） from 1-alkyl-2-chloro-1H-indole-3-carbaldehydes（3a―3d） was described.The Williamson reactions and esterification reactions were performed and the oxime-ethers and oxime-esters were synthesized,respectively.The new synthesized compounds（3a―11d） were characterized by 1H NMR,IR,MS,and elemental analysis.
基金Project 20572040 was supported by National Natural Science Foundation of China
文摘O-Alkylation of oximes with N-vinylpyrrolidin-2-one or N-methyl-N-vinylacetamide was efficiently initiated by a catalytic amount of cerium（Ⅳ） ammonium nitrate（CAN）,giving the corresponding oxime ether derivatives in good yield.
基金supported by the National Natural Science Foundation of China(Nos.22101237,22171233,22001220)the Open Project Program of Nuclear Medicine and Molecular Imaging Key Laboratory of Sichuan Province(No.HYX21003)+1 种基金the Open Project Program of State Key Laboratory of Natural and Biomimetic Drugs(No.K202105)the Scientific Fund of Sichuan Province(Nos.2022NSFSC1219,21YYJC0697)。
文摘A novel photoredox-neutral ring-opening pyridylation of non-prefunctionalized cyclic oximes has been accomplished through phosphoranyl radical-mediated N-O/C-C bond cleavages followed by radicalradical coupling.This mild acid-,base-,and oxidant-free protocol provides highly site-selective and efficient access to distally pyridylated alkylnitriles,which could be scale-up synthesized and readily converted into skeletally diverse compounds.Notably,the oxidized ground-state photocatalyst generated via the SET oxidation of the highly reducing excited-state photocatalyst by cyanopyridines might initiate the following phosphoranyl radical-mediated deoxygenative process.
文摘A series of novel flavone-4-oximes[1]were synthesized by the oximation of substituted flavones.The synthesized compounds were characterized by various spectroscopic methods including IR,MASS,NMR spectroscopy.Out of the 14 test compounds screened for their antioxidant activity,compounds such as JGS-VI(a N,N dimethyl benzaldehyde derivative)and JGSVII(a 3,4 dimethoxy benzaldehyde derivative)exhibited antioxidant activity comparable to that of ascorbic acid with its IC50 value at 30.01 Mm as standard following DPPH?method.Compounds such as JGS-II(a Para fluro benzaldehyde derivative),JGS-IV(a Para methyl benzaldehyde derivative)and JGS-V(a thiophene-2-aldehyde derivative)exhibited anti-oxidant activity among all the test compounds screened against ABTS[2]using Quercetin with its IC50 value at 50.24 Mm.
基金Supported by the National Science and Technology Pillar Program of China(No.2011BAE06B01)
文摘A series of rotenone O-alkyl oxime derivatives was designed and synthesized. Their structures were confirmed by elemental analyses, Fourier transform infrared（FTIR） and 1H NMR spectral studies, and the typical crystal structure of rotenone O-ethyl oxime（3b） was determined by X-ray diffraction. The preliminary biological activities of the new compounds were evaluated. The results of bioassays indicate that the title compounds exhibit moderate insecticidal and bactericidal activities. Among the synthesized compounds, compound 3q exhibited 90.0% mortality against M. separata at 1000 μg/mL. Compounds 3b and 3g exhibited both 90.0% inhibition rate against R. solani at 500 μg/mL, respectively.
文摘InCl3 catalyzes the reaction of hydroxylamine hydrochloride with a number of aldehydes and ketones under solvent free condition to afford an efficient method for the synthesis of oximes.*
基金supported by the National Natural Science Foundation of China(Nos.21772107,21901010)Shandong Province Key Research and Development Plan(No.2019GSF108017)。
文摘Oximes derivatives have been vastly used in organic synthesis.In this review,C(sp^(3))-H bond functionalization of oximes derivatives via iminyl radical induced 1,5-hydrogen atom transfer was discussed.According to the different type of products,this review was divided into three parts:(1)C(sp^(3))-H bond functionalization for C-C bond formation.(2)C(sp^(3))-H bond functionalization for C-N bond formation.(3)C(sp^(3))-H bond functionalization for C-S,C-F bond formation.
文摘A convenient copper-catalyzed approach has been developed for the synthesis of substituted spiro-fused pyrazolin-5-ones from readily available cyclopropyl O-acyl ketoximes via an intramolecular N-N bond formation reaction. These catalytic reactions proceed in excellent yields with a broad scope.
文摘A facile and efficient approach to the synthesis of secondary thioamides from ketoximes via Beckmann rearrangement has been established, using phosphorus pentasulfide as a dehydrating and thiating agent. It is also efficient for the preparation of primary thiobenzamide from benzaldoxime. This approach features simple-operation, easy-control and good to excellent yields.
