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2020 Volume 40 Issue 1
2020, 40(1): 1-14
doi: 10.6023/cjoc201907028
Abstract:
Compounds bearing difluoromethylthio (SCF2H) and monofluoromethylthio (SCFH2) groups are potentially important targets in the pharmaceutical and agrochemical fields due to their unique physical and chemical properties. The traditional methods of synthesizing these two kinds of compounds are difluoromethylation and monofluoromethylation of sulfhydryl substrates. However, the limitation of sulfhydryl substrates also limited the application and development of such compounds. Thus, it is still highly desirable to develop new methods for difluoromethylthiolation and monofluoromethylthiolation as well as new types of difluoromethylthiolation and monofluoromethylthiolation reagents. The recent development of direct difluoromethylthiolation and monofluoromethylthiolation reactions is summarized, and the related mechanism are also discussed.
Compounds bearing difluoromethylthio (SCF2H) and monofluoromethylthio (SCFH2) groups are potentially important targets in the pharmaceutical and agrochemical fields due to their unique physical and chemical properties. The traditional methods of synthesizing these two kinds of compounds are difluoromethylation and monofluoromethylation of sulfhydryl substrates. However, the limitation of sulfhydryl substrates also limited the application and development of such compounds. Thus, it is still highly desirable to develop new methods for difluoromethylthiolation and monofluoromethylthiolation as well as new types of difluoromethylthiolation and monofluoromethylthiolation reagents. The recent development of direct difluoromethylthiolation and monofluoromethylthiolation reactions is summarized, and the related mechanism are also discussed.
2020, 40(1): 15-27
doi: 10.6023/cjoc201906007
Abstract:
Pyrazole, an important class of nitrogen-containing five-member hetrocyclic compounds, widely exists in natural products, bio-active molecules and drugs, and it is also a valuable intermediate in organic synthesis. The synthesis of polysubstituted pyrazoles has attracted much attention and developed rapidly in recent years. Herein, the recent research progress in the construction of polysubstituted pyrazoles is summarized.
Pyrazole, an important class of nitrogen-containing five-member hetrocyclic compounds, widely exists in natural products, bio-active molecules and drugs, and it is also a valuable intermediate in organic synthesis. The synthesis of polysubstituted pyrazoles has attracted much attention and developed rapidly in recent years. Herein, the recent research progress in the construction of polysubstituted pyrazoles is summarized.
2020, 40(1): 28-39
doi: 10.6023/cjoc201906023
Abstract:
Based on the atomic economy, mild performance and environment friendly, the in-situ generation of hypervalent iodine reagents has been vastly applied in many significant oxidative reactions and asymmetric catalysis. In this paper, the progress of in-situ generated hypervalent iodine reagents is systematically reviewed, including conception and mechanisms. According to the different reaction types, the application of in-situ generated hapervalent iodine reagent in organic synthesis reaction is summarized, including trivalent iodine reagent, pentavalent iodine reagent and chiral hypervalent iodine reagent. The problem of in-situ generated hapervalent iodine researches is analyzed, and the future development of in-situ hapervalent iodine is prospected.
Based on the atomic economy, mild performance and environment friendly, the in-situ generation of hypervalent iodine reagents has been vastly applied in many significant oxidative reactions and asymmetric catalysis. In this paper, the progress of in-situ generated hypervalent iodine reagents is systematically reviewed, including conception and mechanisms. According to the different reaction types, the application of in-situ generated hapervalent iodine reagent in organic synthesis reaction is summarized, including trivalent iodine reagent, pentavalent iodine reagent and chiral hypervalent iodine reagent. The problem of in-situ generated hapervalent iodine researches is analyzed, and the future development of in-situ hapervalent iodine is prospected.
2020, 40(1): 40-52
doi: 10.6023/cjoc201908034
Abstract:
Under the catalysis of chiral amine methylated quinidine, highly diastereo-and enantioselective cyclopropanation reactions of α-bromoketones with 3-(substituted methylene) oxindoles and electron-deficient 1, 3-dienes have been realized respectively, providing corresponding functionalized 3, 3-spirocyclopropyl oxindoles and vinylcyclopropanes in 46%~99% yields with up to 98% ee and up to 20:1 dr. Thus, a facile and complementary synthetic method for chiral title compounds is successfully develped by the catalytic ammonium ylide strategy.
Under the catalysis of chiral amine methylated quinidine, highly diastereo-and enantioselective cyclopropanation reactions of α-bromoketones with 3-(substituted methylene) oxindoles and electron-deficient 1, 3-dienes have been realized respectively, providing corresponding functionalized 3, 3-spirocyclopropyl oxindoles and vinylcyclopropanes in 46%~99% yields with up to 98% ee and up to 20:1 dr. Thus, a facile and complementary synthetic method for chiral title compounds is successfully develped by the catalytic ammonium ylide strategy.
2020, 40(1): 53-60
doi: 10.6023/cjoc201908017
Abstract:
Four (η6-p-cymene)Ru(Ⅱ) complexes with bidentate NN ligands, (h6-p-cymene)Ru(C5H4N-C5H3N-OH) (1), (η6-p-cymene)Ru(C5H4N-CH2-C5H4N) (2), (η6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH) (3) and (η6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3) (4) were prepared. These complexes were all characterized by1H NMR, 13C NMR and elemental analysis, and complex 2 was further determined by single crystal crystallography. Complexes 1~4 were treated as catalysts for cyclizations of amino alcohols with ketones, and complex 3 exhibited the highest activity. The cyclization reactions proceeded in toluene with 0.5 mol% catalyst loading, and a series of quinolines and pyrroles were synthesized.
Four (η6-p-cymene)Ru(Ⅱ) complexes with bidentate NN ligands, (h6-p-cymene)Ru(C5H4N-C5H3N-OH) (1), (η6-p-cymene)Ru(C5H4N-CH2-C5H4N) (2), (η6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH) (3) and (η6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3) (4) were prepared. These complexes were all characterized by1H NMR, 13C NMR and elemental analysis, and complex 2 was further determined by single crystal crystallography. Complexes 1~4 were treated as catalysts for cyclizations of amino alcohols with ketones, and complex 3 exhibited the highest activity. The cyclization reactions proceeded in toluene with 0.5 mol% catalyst loading, and a series of quinolines and pyrroles were synthesized.
2020, 40(1): 69-77
doi: 10.6023/cjoc201907018
Abstract:
A new method of preparation for natural product Uncinine was reported. According to the method, a series of novel butenolides derivatives were designed and synthesized based on the natural product Uncinine. Most of the synthetic compounds showed significant anti proliferation activity against MGC-803. Among of them, (Z)-5-(4-(tert-butyl)-benzylidene)-3-(morpholinomethyl)furan-2(5H)-one (9l) showed potent anticancer effect with IC50 of 2.9 μmol/L in gastric cancer cell MGC803 and showed good selectivity to gastric cancer cells MGC803, HGC27, SGC7901 and less cytotoxicity in normal gastric epithelial cell line (GES1). The research on the molecular level suggests that the mechanism of compound 9l inducing apoptosis in gastric cancer cells is partially dependent on activation of caspase-9/3.
A new method of preparation for natural product Uncinine was reported. According to the method, a series of novel butenolides derivatives were designed and synthesized based on the natural product Uncinine. Most of the synthetic compounds showed significant anti proliferation activity against MGC-803. Among of them, (Z)-5-(4-(tert-butyl)-benzylidene)-3-(morpholinomethyl)furan-2(5H)-one (9l) showed potent anticancer effect with IC50 of 2.9 μmol/L in gastric cancer cell MGC803 and showed good selectivity to gastric cancer cells MGC803, HGC27, SGC7901 and less cytotoxicity in normal gastric epithelial cell line (GES1). The research on the molecular level suggests that the mechanism of compound 9l inducing apoptosis in gastric cancer cells is partially dependent on activation of caspase-9/3.
2020, 40(1): 61-68
doi: 10.6023/cjoc201905022
Abstract:
An asymmetric 1, 4-addition reaction of diarylphosphines with quinone monoketals was studied. Pincer Pd complex was used as catalyst to generate a series of chiral phosphorus compounds with moderate to good enantioselectivities in high yields.
An asymmetric 1, 4-addition reaction of diarylphosphines with quinone monoketals was studied. Pincer Pd complex was used as catalyst to generate a series of chiral phosphorus compounds with moderate to good enantioselectivities in high yields.
2020, 40(1): 108-114
doi: 10.6023/cjoc201906014
Abstract:
Chalcone derivatives are a kind of 1, 3-diphenylacrylketone compounds with a broad range of biological activities. A series of new thienyl chalcone derivatives bearing piperazine moiety have been designed and prepared based on the principle of bioisosteres and molecular hybridization. Their antibacterial activities against Staphylococcus aureus Rosenbach, Escherichia coli and Bacillus subtilis were evaluated. The results showed that thienyl chalcone derivatives exhibited good selective inhibitory activities against the three tested strains, respectively. Especially, (E)-1-[4-(4-methylcinnamatemethylpiperazinyl)-phenyl]-3-(thien-2-yl)propyl-2-ketene (4b) and (E)-1-{4-[4-(2-oxophenethyl)piperazinyl]phenyl}-3-(thien-2-yl)propyl-2-kete-ne (4e) were found to be very sensitive to Bacillus subtilis, and the minimum inhibitory concentration (MIC) is 4.0 μg/mL against Bacillus subtilis.
Chalcone derivatives are a kind of 1, 3-diphenylacrylketone compounds with a broad range of biological activities. A series of new thienyl chalcone derivatives bearing piperazine moiety have been designed and prepared based on the principle of bioisosteres and molecular hybridization. Their antibacterial activities against Staphylococcus aureus Rosenbach, Escherichia coli and Bacillus subtilis were evaluated. The results showed that thienyl chalcone derivatives exhibited good selective inhibitory activities against the three tested strains, respectively. Especially, (E)-1-[4-(4-methylcinnamatemethylpiperazinyl)-phenyl]-3-(thien-2-yl)propyl-2-ketene (4b) and (E)-1-{4-[4-(2-oxophenethyl)piperazinyl]phenyl}-3-(thien-2-yl)propyl-2-kete-ne (4e) were found to be very sensitive to Bacillus subtilis, and the minimum inhibitory concentration (MIC) is 4.0 μg/mL against Bacillus subtilis.
2020, 40(1): 125-132
doi: 10.6023/cjoc201811025
Abstract:
The photo-reversible isomerization property of the azo bend liquid crystal has become a hot topic in the research opt-electronic information materials, but its slow light response has become a key factor restricting its development. At present, the azo bond of the bent liquid crystal compound is far from the central nucleus, and the photo isomerization response time is long, mostly over minutes, which is not conducive to the application research of the photosensitive device. In this work, methyl-1, 3-m-phenylenediamine was chosen the central nucleus. The azo bond is adjacent to both sides of the central ring and the terminal group is an alkyl chain. A series of novel curved bisazo benzene liquid crystal compounds were designed and synthesized, in order to shorten the light response time. The molecular structures of these compounds were identified by IR, 1H NMR, 13C NMR and ICP-MS spectroscopy. The phase transition temperature and phase texture of the liquid crystals were determined by differential scanning calorimeter (DSC) and polarized light microscopy (POM). The photo isomerization performance of 2-methyl-1, 3-bis(4-((4-heptylphenyl)ester)-1-(E)-azophenyl)benzene (2c) was determined by UV-Vis absorption spectroscopy. The photo isomerism and response time of the liquid crystal compound and the doped nematic liquid crystal material were measured by UV-Vis spectrometer and polarizing microscope (POM). The experimental results show that all the curved bisazo benzene liquid crystal compounds designed and synthesized have the smectic phase and the phase temperature range is wide. The photo induced isomerization response time of compound 2c in the liquid crystal state of smectic phase and nematic phase is 2~3 s, and the recovery time of liquid crystal state in sunlight is 3~4 s, which can be reached in diluted ethyl acetate solution for 10 s. This type of bent bisazo liquid crystal compound has a relatively fast photo induced heterogeneous response speed.
The photo-reversible isomerization property of the azo bend liquid crystal has become a hot topic in the research opt-electronic information materials, but its slow light response has become a key factor restricting its development. At present, the azo bond of the bent liquid crystal compound is far from the central nucleus, and the photo isomerization response time is long, mostly over minutes, which is not conducive to the application research of the photosensitive device. In this work, methyl-1, 3-m-phenylenediamine was chosen the central nucleus. The azo bond is adjacent to both sides of the central ring and the terminal group is an alkyl chain. A series of novel curved bisazo benzene liquid crystal compounds were designed and synthesized, in order to shorten the light response time. The molecular structures of these compounds were identified by IR, 1H NMR, 13C NMR and ICP-MS spectroscopy. The phase transition temperature and phase texture of the liquid crystals were determined by differential scanning calorimeter (DSC) and polarized light microscopy (POM). The photo isomerization performance of 2-methyl-1, 3-bis(4-((4-heptylphenyl)ester)-1-(E)-azophenyl)benzene (2c) was determined by UV-Vis absorption spectroscopy. The photo isomerism and response time of the liquid crystal compound and the doped nematic liquid crystal material were measured by UV-Vis spectrometer and polarizing microscope (POM). The experimental results show that all the curved bisazo benzene liquid crystal compounds designed and synthesized have the smectic phase and the phase temperature range is wide. The photo induced isomerization response time of compound 2c in the liquid crystal state of smectic phase and nematic phase is 2~3 s, and the recovery time of liquid crystal state in sunlight is 3~4 s, which can be reached in diluted ethyl acetate solution for 10 s. This type of bent bisazo liquid crystal compound has a relatively fast photo induced heterogeneous response speed.
2020, 40(1): 133-139
doi: 10.6023/cjoc201907002
Abstract:
Herein, the visible-light-induced α-C(sp3)—H amination reactions of tertiary amines were reported. By using readily available 1, 3-dioxoisoindolin-2-yl benzoate as precursor of N-radical and blue LEDs as green and sustainable energy source, the α-C(sp3)—H bonds of various N, N-dimethylaniline derivatives were aminated directly. Based on radical trapping experiment and documented literature, a mechanism involving radicals coupling was proposed. This method featured in mild reaction conditions and good functional group tolerance, which provides a simple and practical protocol to the modification of tertiary amines.
Herein, the visible-light-induced α-C(sp3)—H amination reactions of tertiary amines were reported. By using readily available 1, 3-dioxoisoindolin-2-yl benzoate as precursor of N-radical and blue LEDs as green and sustainable energy source, the α-C(sp3)—H bonds of various N, N-dimethylaniline derivatives were aminated directly. Based on radical trapping experiment and documented literature, a mechanism involving radicals coupling was proposed. This method featured in mild reaction conditions and good functional group tolerance, which provides a simple and practical protocol to the modification of tertiary amines.
2020, 40(1): 140-148
doi: 10.6023/cjoc201905054
Abstract:
A photocatalyzed method for the synthesis of δ-ketonitriles from the reaction of diaryl allyl alcohols with bromoacetonitrile is developed. The result of control experiments indicates that the reaction might proceed via a free radical mechanism and bromoacetonitrile was the source of cyanomethyl radical.
A photocatalyzed method for the synthesis of δ-ketonitriles from the reaction of diaryl allyl alcohols with bromoacetonitrile is developed. The result of control experiments indicates that the reaction might proceed via a free radical mechanism and bromoacetonitrile was the source of cyanomethyl radical.
2020, 40(1): 149-155
doi: 10.6023/cjoc201905045
Abstract:
A new general synthetic route towards benzylisoquinoline alkaloids was developed. The key step of this route is Cu-catalyzed cascade oxidation-aromatization of 1-benzyl-3, 4-dihydroisoquinolines. The three benzylisoquinoline alkaloids such as neolitacumonine, mollinedine and papaverine were synthesized starting from piperonaldehyde and 3, 4-dimethoxybenzaldehyde by 8 steps in 42%, 37% and 37% overall yields, respectively.
A new general synthetic route towards benzylisoquinoline alkaloids was developed. The key step of this route is Cu-catalyzed cascade oxidation-aromatization of 1-benzyl-3, 4-dihydroisoquinolines. The three benzylisoquinoline alkaloids such as neolitacumonine, mollinedine and papaverine were synthesized starting from piperonaldehyde and 3, 4-dimethoxybenzaldehyde by 8 steps in 42%, 37% and 37% overall yields, respectively.
2020, 40(1): 156-161
doi: 10.6023/cjoc201905040
Abstract:
In the deep eutectic solvent which composed of choline chloride and zinc chloride, a series of 2, 4-disubstituted quinolines were synthesized via cyclization coupling of 2-aminoacetophenone and aromatic alkyne. When the molar ratio of choline chloride and zinc chloride was 1:2, the yield up to 98% was achieved at 80℃ for 3 h. The method does not need additional catalyst, and has the advantages of mild reaction conditions, simple operation and a wide range of substrates.
In the deep eutectic solvent which composed of choline chloride and zinc chloride, a series of 2, 4-disubstituted quinolines were synthesized via cyclization coupling of 2-aminoacetophenone and aromatic alkyne. When the molar ratio of choline chloride and zinc chloride was 1:2, the yield up to 98% was achieved at 80℃ for 3 h. The method does not need additional catalyst, and has the advantages of mild reaction conditions, simple operation and a wide range of substrates.
2020, 40(1): 162-174
doi: 10.6023/cjoc201905043
Abstract:
A series of novel carbazole-based mono-/bis-thiocarbohydrazone derivatives were synthesized. Their structures were characterized by IR, 1H NMR, 13C NMR spectra and elemental analysis. The inhibitory activities of the target compounds against Cdc25B/PTP1B were evaluated, and the relationship between structure and activity was discussed. The results showed that most of the target compounds had good inhibitory activity against Cdc25B and PTP1B. Among them, 1, 5-bis[(9-pentyl-3-carbazolyl)methylene]thiocarbohydrazone (4d) had the highest inhibitory activity against Cdc25B with IC50=(0.23±0.02) μg/mL, and 1, 5-bis[(9-ethyl-3-carbazolyl)methylene]thiocarbohydrazone (4a) had the highest inhibitory activity against PTP1B with IC50=(1.00±0.16) μg/mL. Molecular docking and density functional theory (DFT) calculations of the target compounds 4a and 4d were performed. Molecular docking results indicated that the target compounds 4d and 4a entered the active sites of Cdc25B and PTP1B enzymes, respectively, and thiocarbohydrazone and carbazole groups play the importent role of activity.
A series of novel carbazole-based mono-/bis-thiocarbohydrazone derivatives were synthesized. Their structures were characterized by IR, 1H NMR, 13C NMR spectra and elemental analysis. The inhibitory activities of the target compounds against Cdc25B/PTP1B were evaluated, and the relationship between structure and activity was discussed. The results showed that most of the target compounds had good inhibitory activity against Cdc25B and PTP1B. Among them, 1, 5-bis[(9-pentyl-3-carbazolyl)methylene]thiocarbohydrazone (4d) had the highest inhibitory activity against Cdc25B with IC50=(0.23±0.02) μg/mL, and 1, 5-bis[(9-ethyl-3-carbazolyl)methylene]thiocarbohydrazone (4a) had the highest inhibitory activity against PTP1B with IC50=(1.00±0.16) μg/mL. Molecular docking and density functional theory (DFT) calculations of the target compounds 4a and 4d were performed. Molecular docking results indicated that the target compounds 4d and 4a entered the active sites of Cdc25B and PTP1B enzymes, respectively, and thiocarbohydrazone and carbazole groups play the importent role of activity.
2020, 40(1): 78-83
doi: 10.6023/cjoc201908001
Abstract:
A green and scalable oxidation of 2-ethyl-3-methylpyrazine (EMP) by tert-butylhydroperoxide was investigated with a catalytic system of cobalt(Ⅱ) and N-containing ligand. The effects of catalyst, ligand, solvent and temperature were compared, and the catalysis system of cobalt(Ⅱ) acetylacetonate and 2, 2-bipyridine gave the highest selectivity. Mechanistic study of this catalysis system suggested that the oxidation of EMP followed a free radical oxidation pathway, and a homogeneous reaction kinetics model was established to calculate the reaction rate constant and activation energy. The scale-up of the oxidation system was performed to check the scalability of the oxidation reaction, and the temperature control of the system was the key part of the process.
A green and scalable oxidation of 2-ethyl-3-methylpyrazine (EMP) by tert-butylhydroperoxide was investigated with a catalytic system of cobalt(Ⅱ) and N-containing ligand. The effects of catalyst, ligand, solvent and temperature were compared, and the catalysis system of cobalt(Ⅱ) acetylacetonate and 2, 2-bipyridine gave the highest selectivity. Mechanistic study of this catalysis system suggested that the oxidation of EMP followed a free radical oxidation pathway, and a homogeneous reaction kinetics model was established to calculate the reaction rate constant and activation energy. The scale-up of the oxidation system was performed to check the scalability of the oxidation reaction, and the temperature control of the system was the key part of the process.
Discovery of a Novel FGFR4 Selective Inhibitor via Structure-Activity Relationship Studies of FGF401
2020, 40(1): 84-94
doi: 10.6023/cjoc201904073
Abstract:
A set of analogues of FRF401 were designed and synthesized, and their FGFR4 inhibition and antitumor activity as well as the structure-activity relationship (SAR) studies were screened. It was found that N-(5-cyano-4-((2-methoxyethyl)-amino)pyridin-2-yl)-7-formyl-6-((N-methyltetrahydro-2H-pyran-4-carboxamido)methyl)-1, 2, 3, 4-tetrahydro-1, 8-naphthyridine-1-carboxamide (8ac) not only showed superior FGFR4 inhibitory activity compared with FGF401 and excellent selectivity in enzymatic and cellular level, but also dramatically inhibited tumor growth and induced tumor regression in hepatocellular carcinoma xenograft model.
A set of analogues of FRF401 were designed and synthesized, and their FGFR4 inhibition and antitumor activity as well as the structure-activity relationship (SAR) studies were screened. It was found that N-(5-cyano-4-((2-methoxyethyl)-amino)pyridin-2-yl)-7-formyl-6-((N-methyltetrahydro-2H-pyran-4-carboxamido)methyl)-1, 2, 3, 4-tetrahydro-1, 8-naphthyridine-1-carboxamide (8ac) not only showed superior FGFR4 inhibitory activity compared with FGF401 and excellent selectivity in enzymatic and cellular level, but also dramatically inhibited tumor growth and induced tumor regression in hepatocellular carcinoma xenograft model.
2020, 40(1): 95-107
doi: 10.6023/cjoc201908021
Abstract:
Polypharmacology has emerged as a promising approach to drug discovery, especially antitumor drug. This study reports the design, synthesis, and biological evaluation of novel phosphatidylinositol 3-kinases (PI3Ks) and histone deacetylases (HDACs) dual inhibitors on the basis of GSK2126458 under clinical evaluation and vorinostat approved. Among these hybrid molecules, GYB-4 and GYB-5 possessed potent inhibition against both PI3Kα (1.0 and 1.3 nmol/L, respectively) and HDAC1 (4.2 and 4.8 nmol/L, respectively). Antiproliferative assays with HCT116, PC3 and A2780 cell lines subsequently were performed. The structure-activity relationship study will guide to optimization of dual PI3K and HDAC inhibitors.
Polypharmacology has emerged as a promising approach to drug discovery, especially antitumor drug. This study reports the design, synthesis, and biological evaluation of novel phosphatidylinositol 3-kinases (PI3Ks) and histone deacetylases (HDACs) dual inhibitors on the basis of GSK2126458 under clinical evaluation and vorinostat approved. Among these hybrid molecules, GYB-4 and GYB-5 possessed potent inhibition against both PI3Kα (1.0 and 1.3 nmol/L, respectively) and HDAC1 (4.2 and 4.8 nmol/L, respectively). Antiproliferative assays with HCT116, PC3 and A2780 cell lines subsequently were performed. The structure-activity relationship study will guide to optimization of dual PI3K and HDAC inhibitors.
2020, 40(1): 115-124
doi: 10.6023/cjoc201907050
Abstract:
An alkali salt-catalyzed highly efficient aza-Michael addition of 1, 2, 4-triazole to α, β-unsaturated ketones and imides has been developed, giving the desired products in moderate to excellent yields. The salient features of this reaction involve readily available starting materials, good substrate scope, mild condition, high efficiency and ease of scale-up. The product can be transformed into corresponding γ-aminoalcohol.
An alkali salt-catalyzed highly efficient aza-Michael addition of 1, 2, 4-triazole to α, β-unsaturated ketones and imides has been developed, giving the desired products in moderate to excellent yields. The salient features of this reaction involve readily available starting materials, good substrate scope, mild condition, high efficiency and ease of scale-up. The product can be transformed into corresponding γ-aminoalcohol.
2020, 40(1): 175-180
doi: 10.6023/cjoc201907042
Abstract:
The host-guest interaction was qualified as an ideal drive force to form stable inclusion complexes with macrocyclic host molecules in aqueous solution. Herein, a multi-responsive supramolecular hydrogel was constructed based on a functionalized benzimidazole derivative guest (M) with soluble pillar[5]arene as a host group. The mechanism of hydrogel formation was explored by the 1H NMR, 2D NOESY and scanning electron microscope (SEM) in depth study. Interestingly, host-guest inclusion, the ordered "exo-wall" π-π interaction and hierarchical stacking of pillar[5]arene was indispensable to obtain the supramolecular hydrogel, which endowed the gel system with response to temperature change/chemical stimuli. Upon addition of competitive guests adiponitrile (ADN)/paraquat (PQ), pillar[5]arene-based hydrogel could be converted into sol. Herein, the organic molecules could be selectively recognized by the hydrogel.
The host-guest interaction was qualified as an ideal drive force to form stable inclusion complexes with macrocyclic host molecules in aqueous solution. Herein, a multi-responsive supramolecular hydrogel was constructed based on a functionalized benzimidazole derivative guest (M) with soluble pillar[5]arene as a host group. The mechanism of hydrogel formation was explored by the 1H NMR, 2D NOESY and scanning electron microscope (SEM) in depth study. Interestingly, host-guest inclusion, the ordered "exo-wall" π-π interaction and hierarchical stacking of pillar[5]arene was indispensable to obtain the supramolecular hydrogel, which endowed the gel system with response to temperature change/chemical stimuli. Upon addition of competitive guests adiponitrile (ADN)/paraquat (PQ), pillar[5]arene-based hydrogel could be converted into sol. Herein, the organic molecules could be selectively recognized by the hydrogel.
2020, 40(1): 181-185
doi: 10.6023/cjoc201907039
Abstract:
Hydrazine is an important raw material and catalyst in chemical industry. However, hydrazine is very harmful to human organs. A new type of probe was developed based on the synergistic effect. Two recognition sites were introduced into the probe to improve performance to hydrazine, which has good specificity to hydrazine. The limit of detection (LOD) for N2H4 was 0.05~10.0 μmol·L-1. Moreover, the probe could detect N2H4 in BT-474 cells.
Hydrazine is an important raw material and catalyst in chemical industry. However, hydrazine is very harmful to human organs. A new type of probe was developed based on the synergistic effect. Two recognition sites were introduced into the probe to improve performance to hydrazine, which has good specificity to hydrazine. The limit of detection (LOD) for N2H4 was 0.05~10.0 μmol·L-1. Moreover, the probe could detect N2H4 in BT-474 cells.
2020, 40(1): 186-193
doi: 10.6023/cjoc201908019
Abstract:
A series of phenanthro[9, 10-d]imidazole (CA1~CA6) or 4, 5-diphenyl imidazole (CB1~CB6) modified coumarin derivatives with different electron-donating substitutes were synthesized, and their fluorescences in organic solvent and solid were primarily explored. The results showed that the amino substituents in coumarin skelton enabled strong fluorescence in dichloromethane, while hydroxyl-, butoxyl-, or non-substituted derivatives showed very weak emission in dichloromethane. Meanwhile, phenanthro[9, 10-d]imidazole modified coumarin dervatives CA1~CA5 exhibited stronger fluorescence than that of 4, 5-diphenyl imidazole modified ones. Additionally, the strenghts of intramolecular hydrogen bond as well as the dihedral angles of the imidazole moiety and coumarin ring affected the optical properties of these dyes.
A series of phenanthro[9, 10-d]imidazole (CA1~CA6) or 4, 5-diphenyl imidazole (CB1~CB6) modified coumarin derivatives with different electron-donating substitutes were synthesized, and their fluorescences in organic solvent and solid were primarily explored. The results showed that the amino substituents in coumarin skelton enabled strong fluorescence in dichloromethane, while hydroxyl-, butoxyl-, or non-substituted derivatives showed very weak emission in dichloromethane. Meanwhile, phenanthro[9, 10-d]imidazole modified coumarin dervatives CA1~CA5 exhibited stronger fluorescence than that of 4, 5-diphenyl imidazole modified ones. Additionally, the strenghts of intramolecular hydrogen bond as well as the dihedral angles of the imidazole moiety and coumarin ring affected the optical properties of these dyes.
2020, 40(1): 194-200
doi: 10.6023/cjoc201907001
Abstract:
An acceptor-acceptor polymer HFTBT-DA865 based on dithiophene benzothiadiazole and isoindigo units has been synthesized by Stille polymerizaiton condensation reaction assisted with microwave. The thermal stability, photophysical properties, electrochemical properties and bulk heterojunction solar cells have been researched in details. This polymer is easily soluble in o-dichlorobenzene, o-xylene and so on, and has excellent solution processing properties. Its 5% thermal decompostion is 389℃ and glass transition temperature is 168℃, which show that the polymer has excellent thermal stability. By optimizing spin coating speed and temperature, the maximum photoelectric conversion efficiency of the polymer solar cell based on HFTBT-DA865 is 2.28%, the open circuit voltage is 0.83 V, the short circuit current is -5.70 mA/cm2, and the filling factor is 48.9%. Electrochemical performance and density functional theory estimates show that the lowest unoccupied molecular orbital (LUMO) values and the planarity of polymer and PC71BM may be the key factors affecting the low power conversion efficiency (PCE). The device performance can be further improved by further optimization of the monomer structure and the acceptor materials. This study about the properties of bulk heterojunction (BHJ) polymer solar cell based on acceptor-acceptor (A-A) typed conjugated polymer shows that this type polymer is a potential polymer solar cell material.
An acceptor-acceptor polymer HFTBT-DA865 based on dithiophene benzothiadiazole and isoindigo units has been synthesized by Stille polymerizaiton condensation reaction assisted with microwave. The thermal stability, photophysical properties, electrochemical properties and bulk heterojunction solar cells have been researched in details. This polymer is easily soluble in o-dichlorobenzene, o-xylene and so on, and has excellent solution processing properties. Its 5% thermal decompostion is 389℃ and glass transition temperature is 168℃, which show that the polymer has excellent thermal stability. By optimizing spin coating speed and temperature, the maximum photoelectric conversion efficiency of the polymer solar cell based on HFTBT-DA865 is 2.28%, the open circuit voltage is 0.83 V, the short circuit current is -5.70 mA/cm2, and the filling factor is 48.9%. Electrochemical performance and density functional theory estimates show that the lowest unoccupied molecular orbital (LUMO) values and the planarity of polymer and PC71BM may be the key factors affecting the low power conversion efficiency (PCE). The device performance can be further improved by further optimization of the monomer structure and the acceptor materials. This study about the properties of bulk heterojunction (BHJ) polymer solar cell based on acceptor-acceptor (A-A) typed conjugated polymer shows that this type polymer is a potential polymer solar cell material.
2020, 40(1): 201-208
doi: 10.6023/cjoc201907027
Abstract:
Four natural chalcones, bartericin A (1), 2', 6'-dihydroxy-5'-(2"-hydroxy-3"-methyl-3"-butenyl)-4'-methoxychalcone (2), xanthohumol D (3) and angusticornin B (4) were synthesized for the first time and all of them shared 5'-hydroxyisoprenyl group in common. One of their deriative, compound 6, was also prepared in order to investigate the effect of different functional group in natural products on antibacterial activity of the core structure. After confirming their structures by 1H NMR, 13C NMR, IR and HRMS, 1~4 and 6 were evaluated for their antibacterial activities against Bacillus subtilis[CMCC(B)63 501], Staphylococcus aureus[CMCC(B)260003], Escherichia coli[CMCC(B)44102] and Pseudomonas aeruginosa[CMCC(B)10104]. In this assay micro-dilution method was employed. The results showed that compounds 1, 4 and 6 exhibited moderate activity against gram-positive bacteria Bacillus subtilis and Staphylococcus aureus. Meanwhile compound 3 showed significant activity towards Bacillus subtilis but no activity to the other 3 strains even in 200 μg/mL concentration.
Four natural chalcones, bartericin A (1), 2', 6'-dihydroxy-5'-(2"-hydroxy-3"-methyl-3"-butenyl)-4'-methoxychalcone (2), xanthohumol D (3) and angusticornin B (4) were synthesized for the first time and all of them shared 5'-hydroxyisoprenyl group in common. One of their deriative, compound 6, was also prepared in order to investigate the effect of different functional group in natural products on antibacterial activity of the core structure. After confirming their structures by 1H NMR, 13C NMR, IR and HRMS, 1~4 and 6 were evaluated for their antibacterial activities against Bacillus subtilis[CMCC(B)63 501], Staphylococcus aureus[CMCC(B)260003], Escherichia coli[CMCC(B)44102] and Pseudomonas aeruginosa[CMCC(B)10104]. In this assay micro-dilution method was employed. The results showed that compounds 1, 4 and 6 exhibited moderate activity against gram-positive bacteria Bacillus subtilis and Staphylococcus aureus. Meanwhile compound 3 showed significant activity towards Bacillus subtilis but no activity to the other 3 strains even in 200 μg/mL concentration.
2020, 40(1): 215-220
doi: 10.6023/cjoc201908008
Abstract:
In order to develop fluorogenic enzyme substrate for quick diaganosis of mucopolysaccharidosis type I, 6-chloro-4-methylumbelliferyl-α-L-idopyranosiduronic acid was synthesized from commercially available D-glucurono-6, 3-lactone. Firstly, 1, 2, 3, 4-tetra-O-acetyl-β-D-glucoronate methyl ester was brominated and subsequently reduced with radical reaction to give 1, 2, 3, 4-tetra-O-acetyl-L-idopyranuronate methyl ester. Then 6-chloro-4-methylumbelliferyl-α-L-idopyra-nosiduronic acid was synthesized using Mitsunobu reaction as the key step. The related structures of key intermediates were confirmed with X-ray crystallography. The preliminary biological test proved that the synthesized enzyme substrate could be used for quick detection of α-L-iduronidase.
In order to develop fluorogenic enzyme substrate for quick diaganosis of mucopolysaccharidosis type I, 6-chloro-4-methylumbelliferyl-α-L-idopyranosiduronic acid was synthesized from commercially available D-glucurono-6, 3-lactone. Firstly, 1, 2, 3, 4-tetra-O-acetyl-β-D-glucoronate methyl ester was brominated and subsequently reduced with radical reaction to give 1, 2, 3, 4-tetra-O-acetyl-L-idopyranuronate methyl ester. Then 6-chloro-4-methylumbelliferyl-α-L-idopyra-nosiduronic acid was synthesized using Mitsunobu reaction as the key step. The related structures of key intermediates were confirmed with X-ray crystallography. The preliminary biological test proved that the synthesized enzyme substrate could be used for quick detection of α-L-iduronidase.
2020, 40(1): 221-225
doi: 10.6023/cjoc201907054
Abstract:
A series of 5-halogenated 2'-deoxy-2'-β-fluoro-4'-azido pyrimidine nucleosides were synthesized from m-chloro-benzoyl protected 2'-deoxy-2'-β-fluoro-4'-azido uridine via ammonium cerium nitrate (CAN)-mediated halogenation, activation by triazole, amination, and deprotection. In vitro biological evaluation demonstrated that 5-chloro (6a) and 5-iodo (6c) nucleoside derivatives possess potent anti-HBV (hepatitis B virus) activity with low cytotoxicity.
A series of 5-halogenated 2'-deoxy-2'-β-fluoro-4'-azido pyrimidine nucleosides were synthesized from m-chloro-benzoyl protected 2'-deoxy-2'-β-fluoro-4'-azido uridine via ammonium cerium nitrate (CAN)-mediated halogenation, activation by triazole, amination, and deprotection. In vitro biological evaluation demonstrated that 5-chloro (6a) and 5-iodo (6c) nucleoside derivatives possess potent anti-HBV (hepatitis B virus) activity with low cytotoxicity.
2020, 40(1): 226-231
doi: 10.6023/cjoc201906022
Abstract:
New carbonyl ruthenium complexes (μ-o-PPh2C6H4NH)Ru3(μ-H)(CO)9 (2), (o-PPh2C6H4NH)2Ru(CO)2 (3) and (μ-o-PPh2C6H4NMe2)2Ru(CO)3 (4) have been successfully synthesized by using ruthenium carbonyl and o-PPh2C6H4NR2 (R=H, Me) ligand. The three complexes have all been characterized by NMR and IR spectroscopies, elemental analysis and X-ray crystallography. Complexes 2 and 4 could catalyze the hydrogenation of benzaldehyde into benzyl alcohol. However, complex 3 showed no activity. This study reveals a correlation between structure and catalytic property, where the possible deactivation mode for the hydrogenation reaction using the aminophosphino ruthenium catalyst is discussed in view of the experimental work.
New carbonyl ruthenium complexes (μ-o-PPh2C6H4NH)Ru3(μ-H)(CO)9 (2), (o-PPh2C6H4NH)2Ru(CO)2 (3) and (μ-o-PPh2C6H4NMe2)2Ru(CO)3 (4) have been successfully synthesized by using ruthenium carbonyl and o-PPh2C6H4NR2 (R=H, Me) ligand. The three complexes have all been characterized by NMR and IR spectroscopies, elemental analysis and X-ray crystallography. Complexes 2 and 4 could catalyze the hydrogenation of benzaldehyde into benzyl alcohol. However, complex 3 showed no activity. This study reveals a correlation between structure and catalytic property, where the possible deactivation mode for the hydrogenation reaction using the aminophosphino ruthenium catalyst is discussed in view of the experimental work.
2020, 40(1): 232-238
doi: 10.6023/cjoc201908006
Abstract:
In search of novel pyrazole oxime ether derivatives with potent bioactivities, fifteen new pyrazole oxime ethers were designed and synthesized by introducing 1, 3, 4-oxadiazole moiety into the C-4 position of pyrazole based on the structure of fenpyroximate. Their structures were confirmed by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data showed that some title compounds possessed good insecticidal activities against Oriental armyworm or Aphis medicaginis at the concentration of 500 and 100 μg/mL. At 100 μg/mL, compounds 10a, 10e, 10f and 10j displayed 100% mortality rate against Oriental armyworm, and compounds 10g, 10j and 10l showed insecticidal activity against Aphis medicaginis with 100%. In addition, compound 10l had 100% mortality rate against Tetranychus cinnabarinus at 500 μg/mL.
In search of novel pyrazole oxime ether derivatives with potent bioactivities, fifteen new pyrazole oxime ethers were designed and synthesized by introducing 1, 3, 4-oxadiazole moiety into the C-4 position of pyrazole based on the structure of fenpyroximate. Their structures were confirmed by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data showed that some title compounds possessed good insecticidal activities against Oriental armyworm or Aphis medicaginis at the concentration of 500 and 100 μg/mL. At 100 μg/mL, compounds 10a, 10e, 10f and 10j displayed 100% mortality rate against Oriental armyworm, and compounds 10g, 10j and 10l showed insecticidal activity against Aphis medicaginis with 100%. In addition, compound 10l had 100% mortality rate against Tetranychus cinnabarinus at 500 μg/mL.
2020, 40(1): 209-214
doi: 10.6023/cjoc201907041
Abstract:
Six polyketides were isolated from the fermentation broth of an endophytic fungus Trichoderma spirale A725 of the medicinal plant Morinda officinalis by silica gel, reversed phase silica column chromatography, sephadex LH-20 and high performance preparative liquid chromatography. Their structures were elucidated to be 6-hydroxy-4-isopropyl-1, 8-dimethyl-spiro[4.5]deca-1, 8-dien-7-one (1), 2-hydroxy-2, 5-dimethyl-7-oxo-5, 7-dihydro-2H-furo[3, 4-b]pyran-4-carboxylicacid (2), 3-ethyl-4-hydroxy-6-methyl-2H-pyran-2-one (3), harzialactone A (4), 3-hydroxy-5-(4-hydroxybenzyl)dihydrofuran-2(3H)-one (5), and 4-acetyl-3-hydroxy-6-methyl-pyran-2-one (6) on the basis of extensive spectral analysis. Among them, compounds 1 and 2 were new compounds, and compound 3 was a new natural product. Moreover, the cytotoxicities of compounds 1~6 were evaluated against four cancer cell lines (Hep G-2, MCF-7, SF-268 and A549). However, none of them exhibited cytotoxic activity against the tested tumor cells.
Six polyketides were isolated from the fermentation broth of an endophytic fungus Trichoderma spirale A725 of the medicinal plant Morinda officinalis by silica gel, reversed phase silica column chromatography, sephadex LH-20 and high performance preparative liquid chromatography. Their structures were elucidated to be 6-hydroxy-4-isopropyl-1, 8-dimethyl-spiro[4.5]deca-1, 8-dien-7-one (1), 2-hydroxy-2, 5-dimethyl-7-oxo-5, 7-dihydro-2H-furo[3, 4-b]pyran-4-carboxylicacid (2), 3-ethyl-4-hydroxy-6-methyl-2H-pyran-2-one (3), harzialactone A (4), 3-hydroxy-5-(4-hydroxybenzyl)dihydrofuran-2(3H)-one (5), and 4-acetyl-3-hydroxy-6-methyl-pyran-2-one (6) on the basis of extensive spectral analysis. Among them, compounds 1 and 2 were new compounds, and compound 3 was a new natural product. Moreover, the cytotoxicities of compounds 1~6 were evaluated against four cancer cell lines (Hep G-2, MCF-7, SF-268 and A549). However, none of them exhibited cytotoxic activity against the tested tumor cells.
2020, 40(1): 239-240
doi: 10.6023/cjoc202000001
Abstract:
2020, 40(1): 241-242
doi: 10.6023/cjoc202000002
Abstract:
2020, 40(1): 243-244
doi: 10.6023/cjoc202000003
Abstract:
2020, 40(1): 245-246
doi: 10.6023/cjoc202000004
Abstract:
2020, 40(1): 247-248
doi: 10.6023/cjoc202000005
Abstract:
