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2016 Volume 36 Issue 11
2016, 36(11): 2513-2529
doi: 10.6023/cjoc201605034
Abstract:
Hypervalent iodine chemistry has experienced explosive development over the past 30 years. Being a class of mild, efficient and environmentally benign nonmetal oxidants, hypervalent iodine regents, especially iodine (Ⅲ) oxidants have been widely applied to the construction of various heterocyclic skeletons. In this review, the iodine (Ⅲ)-mediated strategies and methods for the synthesis of heterocyclic compounds with different ring size were highlighted.
Hypervalent iodine chemistry has experienced explosive development over the past 30 years. Being a class of mild, efficient and environmentally benign nonmetal oxidants, hypervalent iodine regents, especially iodine (Ⅲ) oxidants have been widely applied to the construction of various heterocyclic skeletons. In this review, the iodine (Ⅲ)-mediated strategies and methods for the synthesis of heterocyclic compounds with different ring size were highlighted.
2016, 36(11): 2530-2544
doi: 10.6023/cjoc201605046
Abstract:
Keteniminium salts are unique heteroallenes. The high electrophility and cumulative double bonds render them versatile reactivity. This paper describes the keteniminium salts formed by electrophilic activation of amides or ynamides with non-metal electrophilic reagents. These keteniminium salts mainly undergo electrophilic addition, eletrophilic substitution, cycloaddition with various nucleophiles. In past few years, the study of keteniminium induced electrophilic rearrangement has progressed rapidly. The newly developed rearrangement transformations are also described here.
Keteniminium salts are unique heteroallenes. The high electrophility and cumulative double bonds render them versatile reactivity. This paper describes the keteniminium salts formed by electrophilic activation of amides or ynamides with non-metal electrophilic reagents. These keteniminium salts mainly undergo electrophilic addition, eletrophilic substitution, cycloaddition with various nucleophiles. In past few years, the study of keteniminium induced electrophilic rearrangement has progressed rapidly. The newly developed rearrangement transformations are also described here.
2016, 36(11): 2545-2558
doi: 10.6023/cjoc201605040
Abstract:
The high selective and sensitive detection of pyrophosphate anion has attracted increasing attention in recent years due to its significance in the fields of biology, environment and clinic diagnostics. The recent advances of the new sensing ensembles for PPi based on the sensing materials are highlighted, and the sensing ensembles are categorized by sensing materials involving nano materials, conjugated polyelectrolytes/polymers, lipidosome, aggregation-induced luminescent molecules and other sensing materials. In the end, the development tendency of the sensing ensembles for PPi is prospected.
The high selective and sensitive detection of pyrophosphate anion has attracted increasing attention in recent years due to its significance in the fields of biology, environment and clinic diagnostics. The recent advances of the new sensing ensembles for PPi based on the sensing materials are highlighted, and the sensing ensembles are categorized by sensing materials involving nano materials, conjugated polyelectrolytes/polymers, lipidosome, aggregation-induced luminescent molecules and other sensing materials. In the end, the development tendency of the sensing ensembles for PPi is prospected.
2016, 36(11): 2559-2582
doi: 10.6023/cjoc201606012
Abstract:
The recognition and detection of trace fluoride ions in vivo and vitro have attracted great attention in recent years. More and more new fluorescent probes (FP) for fluoride ion detection have been designed and synthesized due to their advantages, such as high sensitivity, good selectivity and convenient operation. According to the different structural features and recognition mechanism, fluoride ion FP can be classified into two categories as deprotonation and reaction type. The new progress especially in recent three years on their molecular design, synthesis and application is reviewed on the viewpoint of green chemistry. The future trend of fluoride ion FP is also prospected.
The recognition and detection of trace fluoride ions in vivo and vitro have attracted great attention in recent years. More and more new fluorescent probes (FP) for fluoride ion detection have been designed and synthesized due to their advantages, such as high sensitivity, good selectivity and convenient operation. According to the different structural features and recognition mechanism, fluoride ion FP can be classified into two categories as deprotonation and reaction type. The new progress especially in recent three years on their molecular design, synthesis and application is reviewed on the viewpoint of green chemistry. The future trend of fluoride ion FP is also prospected.
2016, 36(11): 2583-2601
doi: 10.6023/cjoc201603037
Abstract:
Chirality is a common phenomenon in nature. Designing and synthesis of novel artificial receptors to emulate the molecular recognition in living organism has become the challenging forefront of bioorganic chemistry and supramolecular chemistry. Molecular tweezers have been widely applied in chiral molecular recognition and detection for its easily modified structure. Molecular tweezers and their chiral recognition properties detected by spectrometry, chromatography and mass spectrometry are summarized in this paper, and the prospect of molecular tweezers is also discussed.
Chirality is a common phenomenon in nature. Designing and synthesis of novel artificial receptors to emulate the molecular recognition in living organism has become the challenging forefront of bioorganic chemistry and supramolecular chemistry. Molecular tweezers have been widely applied in chiral molecular recognition and detection for its easily modified structure. Molecular tweezers and their chiral recognition properties detected by spectrometry, chromatography and mass spectrometry are summarized in this paper, and the prospect of molecular tweezers is also discussed.
2016, 36(11): 2602-2618
doi: 10.6023/cjoc201605020
Abstract:
Squaraine (SQ) small molecules have been considered as efficient photoactive materials for organic photovoltaic (OPV) cells due to their simple synthetic routes, high absorption coefficients with tunable bandgaps and bandwidths in the visible-near infrared region, as well as high photochemical and thermal stabilities. The SQ donor and fullerene acceptor based OPV devices have realized the power conversion efficiencies of over 8%. In this paper, the progress of SQ donor and fullerene acceptor based OPV cells is reviewed, the effect of molecular structure, molecular aggregation and film morphology on the device performance is systematically summarized. The applied field of SQ donors in OPV cells is widened, and some proposals for future study are also given.
Squaraine (SQ) small molecules have been considered as efficient photoactive materials for organic photovoltaic (OPV) cells due to their simple synthetic routes, high absorption coefficients with tunable bandgaps and bandwidths in the visible-near infrared region, as well as high photochemical and thermal stabilities. The SQ donor and fullerene acceptor based OPV devices have realized the power conversion efficiencies of over 8%. In this paper, the progress of SQ donor and fullerene acceptor based OPV cells is reviewed, the effect of molecular structure, molecular aggregation and film morphology on the device performance is systematically summarized. The applied field of SQ donors in OPV cells is widened, and some proposals for future study are also given.
2016, 36(11): 2619-2633
doi: 10.6023/cjoc201605024
Abstract:
In recent years, there are many reports about the synthesis of 2, 3-disubstituted indole by cyclization. Most of these approaches are catalyzed by different transition metals and metal-free catalysis conditions using phenylnydrazines, anilines and nitrobenzenes as main substrates. These methods have been a powerful strategy to obtain 2, 3-disubstituted indoles. The recent progress of the synthesis of 2, 3-disubstituted indoles by cyclization with the different substrates systems is summarized.
In recent years, there are many reports about the synthesis of 2, 3-disubstituted indole by cyclization. Most of these approaches are catalyzed by different transition metals and metal-free catalysis conditions using phenylnydrazines, anilines and nitrobenzenes as main substrates. These methods have been a powerful strategy to obtain 2, 3-disubstituted indoles. The recent progress of the synthesis of 2, 3-disubstituted indoles by cyclization with the different substrates systems is summarized.
2016, 36(11): 2634-2650
doi: 10.6023/cjoc201604044
Abstract:
2-Aminobenzoxazole derivatives are a kind of heterocyclic compounds, which play important roles in medicine, biology and material science, and their synthetic methods have attracted much attention. In recent years, many efficient, green synthetic approaches of 2-aminobenzoxazole derivatives using transition-metal or metal-free catalytic systems have been reported. Based on differences of reaction substrates and synthetic methods, the recent advances in the synthesis of 2-aminobenzoxazole derivatives are reviewed.
2-Aminobenzoxazole derivatives are a kind of heterocyclic compounds, which play important roles in medicine, biology and material science, and their synthetic methods have attracted much attention. In recent years, many efficient, green synthetic approaches of 2-aminobenzoxazole derivatives using transition-metal or metal-free catalytic systems have been reported. Based on differences of reaction substrates and synthetic methods, the recent advances in the synthesis of 2-aminobenzoxazole derivatives are reviewed.
2016, 36(11): 2651-2661
doi: 10.6023/cjoc201605022
Abstract:
Fullerene dimers have attracted extensive attention due to their unique structures and fascinating properties. Hundreds of fullerene dimers have been isolated so far, including the singly-bonded fullerene dimers, fullerene dimers connected by electroactive bridges, all-carbon fullerene dimers and unsymmetrical dimers, etc. These new molecular systems have potential applications in the area of artificial photosynthesis, photoelectronic device and supramolecular chemistry. Based on the different structure types, various fullerene dimers reported are summarized and classified in this review. Furthermore, the electrochemistry property of the dimers is discussed and the research trend of this area is also prospected.
Fullerene dimers have attracted extensive attention due to their unique structures and fascinating properties. Hundreds of fullerene dimers have been isolated so far, including the singly-bonded fullerene dimers, fullerene dimers connected by electroactive bridges, all-carbon fullerene dimers and unsymmetrical dimers, etc. These new molecular systems have potential applications in the area of artificial photosynthesis, photoelectronic device and supramolecular chemistry. Based on the different structure types, various fullerene dimers reported are summarized and classified in this review. Furthermore, the electrochemistry property of the dimers is discussed and the research trend of this area is also prospected.
2016, 36(11): 2662-2669
doi: 10.6023/cjoc201604038
Abstract:
2-Imidazolines were synthesized via CuCN-TsOH catalyzed cyclization of nitriles with ethylenediamine in a continuous-flow microreactor. The CuCN-TsOH dissolves in ethylenediamine homogeneously and is a suitable catalyst for the continuous reactions. Under the flow condition, the 2-imidazolines were obtained with high yields in 5 min for most substrates. The "in-tube retention time gradient" (IT-RTG) is achieved in the continuous-flow microreactor, and it is applied in monitoring the reaction progress.
2-Imidazolines were synthesized via CuCN-TsOH catalyzed cyclization of nitriles with ethylenediamine in a continuous-flow microreactor. The CuCN-TsOH dissolves in ethylenediamine homogeneously and is a suitable catalyst for the continuous reactions. Under the flow condition, the 2-imidazolines were obtained with high yields in 5 min for most substrates. The "in-tube retention time gradient" (IT-RTG) is achieved in the continuous-flow microreactor, and it is applied in monitoring the reaction progress.
2016, 36(11): 2670-2676
doi: 10.6023/cjoc201605018
Abstract:
Protein tyrosine phosphatase-1B (PTP1B), a negative regulatory factor of insulin signaling, is recognized as a potent target for the therapy of diabetes. Aimed to provide new scaffold to the development of PTP1B inhibitors and disclose the relationship between configurations of certain positions (3, 4, 5, 6 and 23-position) on the steroidal skeleton and inhibitory activities against PTP1B, a class of lithocholic acid (LCA) mimics were designed and synthesized. In vitro bioassay against PTP1B showed that 3β-hydroxy-4-ene-cholanic acid (17) and 4, 4-dimethyl-3β-hydroxy-5-ene-cholanic acid (19) had activities higher than LCA, reaching (8.50±1.21) and (6.27±1.03) μmol·L-1, respectively. Docking analysis of compounds 17 and 19 illuminated the binding modes to PTP1B. This study provided compounds with new scaffold and valuable structure-activity-relationship (SAR) information for the further study of PTP1B inhibitors.
Protein tyrosine phosphatase-1B (PTP1B), a negative regulatory factor of insulin signaling, is recognized as a potent target for the therapy of diabetes. Aimed to provide new scaffold to the development of PTP1B inhibitors and disclose the relationship between configurations of certain positions (3, 4, 5, 6 and 23-position) on the steroidal skeleton and inhibitory activities against PTP1B, a class of lithocholic acid (LCA) mimics were designed and synthesized. In vitro bioassay against PTP1B showed that 3β-hydroxy-4-ene-cholanic acid (17) and 4, 4-dimethyl-3β-hydroxy-5-ene-cholanic acid (19) had activities higher than LCA, reaching (8.50±1.21) and (6.27±1.03) μmol·L-1, respectively. Docking analysis of compounds 17 and 19 illuminated the binding modes to PTP1B. This study provided compounds with new scaffold and valuable structure-activity-relationship (SAR) information for the further study of PTP1B inhibitors.
2016, 36(11): 2677-2682
doi: 10.6023/cjoc201603036
Abstract:
A simple and powerful procedure for the synthesis of flavones and quinolones was developed by using Ce (SO4)2·4H2O as oxidant, readily available 2'-hydroxychalcones and 2'-aminochalcones as raw materials, and dimethyl sulfoxide (DMSO) as solvent at 110℃. The new procedure is characterized with raw material easy to get, low manufacturing cost, mild reaction condi-tions and high yields.
A simple and powerful procedure for the synthesis of flavones and quinolones was developed by using Ce (SO4)2·4H2O as oxidant, readily available 2'-hydroxychalcones and 2'-aminochalcones as raw materials, and dimethyl sulfoxide (DMSO) as solvent at 110℃. The new procedure is characterized with raw material easy to get, low manufacturing cost, mild reaction condi-tions and high yields.
2016, 36(11): 2683-2688
doi: 10.6023/cjoc201605012
Abstract:
13 New thiophene formyl thiourea derivatives were synthesized via cycloaddition reaction of 3-mercaptobutan-2-one and methyl 3-(substitutedsilyl) propiolate, selective hydrolysis of ester, isothiocyanatation and amination. Their chemical structures were confirmed by 1H NMR, 13C NMR and elemental analysis. The inhibitory activity against Gaeumannomyces graminis var. tritici and Rhizoctonia solani was evaluated in vitro by the plate method. The results indicated that most of thiophene formyl thiourea derivatives showed some inhibitory activity against gaeumannomyces graminis var. tritici. Compound 1-cyclopropyl-3-(4, 5-dimethylthiophene-3-carbonyl) thiourea (8c) gave the best performance and its inhibitory activity was close to the control level of silthiopham in the concentration of 10 mg/L. The structure analysis showed that the steric hindrance of functional group at the second position of the thiophene formyl thioureas had no obvious effect on the inhibitory activity against gaeumannomyces graminis var. tritici.
13 New thiophene formyl thiourea derivatives were synthesized via cycloaddition reaction of 3-mercaptobutan-2-one and methyl 3-(substitutedsilyl) propiolate, selective hydrolysis of ester, isothiocyanatation and amination. Their chemical structures were confirmed by 1H NMR, 13C NMR and elemental analysis. The inhibitory activity against Gaeumannomyces graminis var. tritici and Rhizoctonia solani was evaluated in vitro by the plate method. The results indicated that most of thiophene formyl thiourea derivatives showed some inhibitory activity against gaeumannomyces graminis var. tritici. Compound 1-cyclopropyl-3-(4, 5-dimethylthiophene-3-carbonyl) thiourea (8c) gave the best performance and its inhibitory activity was close to the control level of silthiopham in the concentration of 10 mg/L. The structure analysis showed that the steric hindrance of functional group at the second position of the thiophene formyl thioureas had no obvious effect on the inhibitory activity against gaeumannomyces graminis var. tritici.
2016, 36(11): 2689-2694
doi: 10.6023/cjoc201605027
Abstract:
A high selective fluorescent probe 4 for cyanides was developed based on the Sonogashira reaction between N-butyl-4-bromo-1, 8-naphthalimide and 2-ethynylbenzaldehyde. In CH3CN solution, the probe 4 shows moderate colorimetric and fluorescent response to the cyanides. Upon the addition of TBACN, a new peak at 540 nm appeared in the UV-vis spectra accompanied by an instant colorimetric change from colorless to light violet. No change in the spectral pattern of chemosensor 4 was observed in the presence of other anions. Further, chemosensor 4 showed strong fluorescence with the maximum at 484 nm (λex=390 nm) in a mixture of CH3CN; however, in presence of CN-, a new emission band (λem=600 nm, light brown fluo-rescence) appeared along with a decrease in the emission intensity at 484 nm. Therefore, this process clearly demonstrates that chemosensor 4 can selectively detect cyanide ions by a fluorogenic "on-off" response, which may be attributed to the fact that the electron transfer in 1, 8-naphthalimide is affected by the formation of adducts of anion with carbonyl groups. Moreover, the detailed interference experiments of chemosensor 4 in the mixed solvents were also investigated.
A high selective fluorescent probe 4 for cyanides was developed based on the Sonogashira reaction between N-butyl-4-bromo-1, 8-naphthalimide and 2-ethynylbenzaldehyde. In CH3CN solution, the probe 4 shows moderate colorimetric and fluorescent response to the cyanides. Upon the addition of TBACN, a new peak at 540 nm appeared in the UV-vis spectra accompanied by an instant colorimetric change from colorless to light violet. No change in the spectral pattern of chemosensor 4 was observed in the presence of other anions. Further, chemosensor 4 showed strong fluorescence with the maximum at 484 nm (λex=390 nm) in a mixture of CH3CN; however, in presence of CN-, a new emission band (λem=600 nm, light brown fluo-rescence) appeared along with a decrease in the emission intensity at 484 nm. Therefore, this process clearly demonstrates that chemosensor 4 can selectively detect cyanide ions by a fluorogenic "on-off" response, which may be attributed to the fact that the electron transfer in 1, 8-naphthalimide is affected by the formation of adducts of anion with carbonyl groups. Moreover, the detailed interference experiments of chemosensor 4 in the mixed solvents were also investigated.
2016, 36(11): 2695-2703
doi: 10.6023/cjoc201603027
Abstract:
CO releasing molecules (CORMs) of transition metal carbonyl complexes are emerging as a new interdisciplinary advance of inorganic chemistry, biological medicine and materials chemistry. In this paper, new ionic Fischer carbene carbonyl complexes were devised, in which Cr, Mo and W metals as metallic center carried five CO whilst the quaternary ammonium finely tuned the water solubility of Fc-CORMs. The myoglobin assays showed that one Fc-CORM released at least two molecules of carbon monoxide in well-controlled fashion under physiological conditions. The structure-releasing correlation revealed that the central metal was the key factor governing their carbon monoxide release behavior. The CO release rate of Fc-CORM-Mo (2a~2e) is quicker than Fc-CORM-Cr (1a~1e), much faster than Fc-CORM-W (3a~3e). The antibacterial activity test found that Fc-CORM (1b) with medium CO release rate effectively inhibited the growth and survival of Escherichia coli, with an minimal inhibitory concentration (MIC) value of 30 μmol/L. As for drug-resistant bacteria, Fc-CORM (2a~2e) and Fc-CORM (3a~3e) showed bactericidal activity. Mechanism study indicated that the antibacterial activity relied on the CO release rate of Fc-CORMs.
CO releasing molecules (CORMs) of transition metal carbonyl complexes are emerging as a new interdisciplinary advance of inorganic chemistry, biological medicine and materials chemistry. In this paper, new ionic Fischer carbene carbonyl complexes were devised, in which Cr, Mo and W metals as metallic center carried five CO whilst the quaternary ammonium finely tuned the water solubility of Fc-CORMs. The myoglobin assays showed that one Fc-CORM released at least two molecules of carbon monoxide in well-controlled fashion under physiological conditions. The structure-releasing correlation revealed that the central metal was the key factor governing their carbon monoxide release behavior. The CO release rate of Fc-CORM-Mo (2a~2e) is quicker than Fc-CORM-Cr (1a~1e), much faster than Fc-CORM-W (3a~3e). The antibacterial activity test found that Fc-CORM (1b) with medium CO release rate effectively inhibited the growth and survival of Escherichia coli, with an minimal inhibitory concentration (MIC) value of 30 μmol/L. As for drug-resistant bacteria, Fc-CORM (2a~2e) and Fc-CORM (3a~3e) showed bactericidal activity. Mechanism study indicated that the antibacterial activity relied on the CO release rate of Fc-CORMs.
2016, 36(11): 2704-2708
doi: 10.6023/cjoc201604051
Abstract:
The α-chymotrypsin-catalyzed Friedländer condensation reaction between 2-aminoaryl ketone and α-methylene ketone was firstly reported, and a series of quinoline derivatives were obtained in moderate to excellent yields. This method is easy to operate and the reaction condition is mild, which not only expands the application of the promiscuity of protease, but also has positive significance for promoting the development of the green chemistry.
The α-chymotrypsin-catalyzed Friedländer condensation reaction between 2-aminoaryl ketone and α-methylene ketone was firstly reported, and a series of quinoline derivatives were obtained in moderate to excellent yields. This method is easy to operate and the reaction condition is mild, which not only expands the application of the promiscuity of protease, but also has positive significance for promoting the development of the green chemistry.
2016, 36(11): 2709-2714
doi: 10.6023/cjoc201604060
Abstract:
The Raney-Ni catalyzed N-alkylation for the synthesis of antihistamine drug hydroxyzine (1a) has been developed. The substrate scope was expanded with the optimized reaction conditions, and fourteen diphenylmethyl piperazine derivatives including antihistamine drugs decloxizine (1j), mecilizine (1l), buclizine (1m) and calcium channel blocker lomerizine (1n) were successfully prepared. This Raney-Ni catalyzed N-alkylation was the first protocol that applied in these drugs synthesis. And this research improve its application value in drug synthesis.
The Raney-Ni catalyzed N-alkylation for the synthesis of antihistamine drug hydroxyzine (1a) has been developed. The substrate scope was expanded with the optimized reaction conditions, and fourteen diphenylmethyl piperazine derivatives including antihistamine drugs decloxizine (1j), mecilizine (1l), buclizine (1m) and calcium channel blocker lomerizine (1n) were successfully prepared. This Raney-Ni catalyzed N-alkylation was the first protocol that applied in these drugs synthesis. And this research improve its application value in drug synthesis.
2016, 36(11): 2715-2722
doi: 10.6023/cjoc201605032
Abstract:
A new methodology to high chemoselectively synthesize thiochromone derivatives from β-oxodithioesters and substituted o-bromoacetophenones promoted by CuI/1, 10-phen system based on the substrate-design concept has been developed. This approach has advantages of simple and efficient operation, and high yields.
A new methodology to high chemoselectively synthesize thiochromone derivatives from β-oxodithioesters and substituted o-bromoacetophenones promoted by CuI/1, 10-phen system based on the substrate-design concept has been developed. This approach has advantages of simple and efficient operation, and high yields.
2016, 36(11): 2723-2728
doi: 10.6023/cjoc201603007
Abstract:
Arylnaphthalene lignan lactones, widely distributed in plants, are a class of natural products containing the phenyl-naphthyl skeleton. These compounds have attracted considerable attention of many scientists for decades because of their wide biological activities. In this study, a convenient method is presented for the multiple parallel synthesis of arylnaphthalene lignans. With vanillic acid as starting material, six arylnaphthalene nature products were prepared in the process with 8 steps, via Diels-Alder reaction, Suzuki reaction and Fetizon oxidation as the key reactions.
Arylnaphthalene lignan lactones, widely distributed in plants, are a class of natural products containing the phenyl-naphthyl skeleton. These compounds have attracted considerable attention of many scientists for decades because of their wide biological activities. In this study, a convenient method is presented for the multiple parallel synthesis of arylnaphthalene lignans. With vanillic acid as starting material, six arylnaphthalene nature products were prepared in the process with 8 steps, via Diels-Alder reaction, Suzuki reaction and Fetizon oxidation as the key reactions.
2016, 36(11): 2729-2734
doi: 10.6023/cjoc201605036
Abstract:
In order to systematic study the biological effects of isonucleoside incorporated oligonucleotides, an efficient synthetic process for iso-L-cystidine was investigated in present paper. Using L-ribose as starting material, iso-L-cystidine was obtained in 9 steps and 28.5% overall yield. The key step was the regioselective nucleophilic substitution of 5-O-triphenylmethane-2, 3-O-cyclic sulfate with uracil. After extensive optimization, it was found that using cesium carbonate as base can improve significantly the N-1 glycosidic bond formation and reduce the side reactions. At the same time, a N-1, N-3 doublic 1-deoxyribose substituted iso-L-uridine was identified for the first time. The present reported synthetic process has the merits of mild reaction conditions, easy purified intermediates and high overall yield, which could be used as a general synthetic approach for the preparation other related isonucleoside.
In order to systematic study the biological effects of isonucleoside incorporated oligonucleotides, an efficient synthetic process for iso-L-cystidine was investigated in present paper. Using L-ribose as starting material, iso-L-cystidine was obtained in 9 steps and 28.5% overall yield. The key step was the regioselective nucleophilic substitution of 5-O-triphenylmethane-2, 3-O-cyclic sulfate with uracil. After extensive optimization, it was found that using cesium carbonate as base can improve significantly the N-1 glycosidic bond formation and reduce the side reactions. At the same time, a N-1, N-3 doublic 1-deoxyribose substituted iso-L-uridine was identified for the first time. The present reported synthetic process has the merits of mild reaction conditions, easy purified intermediates and high overall yield, which could be used as a general synthetic approach for the preparation other related isonucleoside.
2016, 36(11): 2735-2738
doi: 10.6023/cjoc201604054
Abstract:
A new flavonoid glycoside, kaempferol-3-O-α-L-rhamnopyranoside-7-O-[6-(4-hydroxy-3-prenybenzoic ester)-β-D-glucopyranosy]-(1→2)-α-L-rhamnopyranoside (1) was isolated from the aerial parts of Liparis bootanensis, together with a known compound kaempferol-3, 7-di-O-α-L-rhamnopyranoside (2) by silica gel column and Pre-HPLC. Their structures were elucidated on the basis of extensive spectroscopic analysis, including HR-ESIMS, 1D and 2D NMR experiments.
A new flavonoid glycoside, kaempferol-3-O-α-L-rhamnopyranoside-7-O-[6-(4-hydroxy-3-prenybenzoic ester)-β-D-glucopyranosy]-(1→2)-α-L-rhamnopyranoside (1) was isolated from the aerial parts of Liparis bootanensis, together with a known compound kaempferol-3, 7-di-O-α-L-rhamnopyranoside (2) by silica gel column and Pre-HPLC. Their structures were elucidated on the basis of extensive spectroscopic analysis, including HR-ESIMS, 1D and 2D NMR experiments.
2016, 36(11): 2739-2742
doi: 10.6023/cjoc201604055
Abstract:
A new aconitine-type diterpenoid alkaloid, villosutine (1), was isolated from the whole plant of Aconitum franchetii var. villosulum, together with four other known aconitine-type diterpenoid alkaloids, one known pyro-type diterpenoid alkaloid and five known franchetine-type diterpenoid alkaloids. Their structures were elucidated on the basis of extensive spectroscopic analy-sis, including HR-ESIMS, 1D and 2D NMR experiments.
A new aconitine-type diterpenoid alkaloid, villosutine (1), was isolated from the whole plant of Aconitum franchetii var. villosulum, together with four other known aconitine-type diterpenoid alkaloids, one known pyro-type diterpenoid alkaloid and five known franchetine-type diterpenoid alkaloids. Their structures were elucidated on the basis of extensive spectroscopic analy-sis, including HR-ESIMS, 1D and 2D NMR experiments.
2016, 36(11): 2743-2745
doi: 10.6023/cjoc201605011
Abstract:
Corosolic acid, a pentacyclic triterpene acid, attracted more and more attention because of the significant anti-diabetes activity. Biocatalysis was applied to modify the structure of corosolic acid to increase the structural diversity of corosolic acid and lay the foundation for screening derivatives with novel structure or better activity. A novel corosolic acid derivative was synthesized by endophytic fungus Umbelopsis isabellina. The structure of the new compound was established by HR-ESIMS and NMR spectrum.
Corosolic acid, a pentacyclic triterpene acid, attracted more and more attention because of the significant anti-diabetes activity. Biocatalysis was applied to modify the structure of corosolic acid to increase the structural diversity of corosolic acid and lay the foundation for screening derivatives with novel structure or better activity. A novel corosolic acid derivative was synthesized by endophytic fungus Umbelopsis isabellina. The structure of the new compound was established by HR-ESIMS and NMR spectrum.
2016, 36(11): 2746-2751
doi: 10.6023/cjoc201605039
Abstract:
3-Cyanomethyl oxoindoles are a kind of important drug intermediates, which can be used to synthesize horsfiline, esermethole and physostigmine and other natural products via the conversion of cyano functional groups. aA domino Heck/cyanation reaction in aqueous was developed to afford 3-cyanomethyl oxoindole compounds. This method, using green medium water instead of organic solvents, without any basic additives, provided a green and efficient new procedure for the synthesis of 3-cyanomethyl oxoindoles.
3-Cyanomethyl oxoindoles are a kind of important drug intermediates, which can be used to synthesize horsfiline, esermethole and physostigmine and other natural products via the conversion of cyano functional groups. aA domino Heck/cyanation reaction in aqueous was developed to afford 3-cyanomethyl oxoindole compounds. This method, using green medium water instead of organic solvents, without any basic additives, provided a green and efficient new procedure for the synthesis of 3-cyanomethyl oxoindoles.
2016, 36(11): 2752-2756
doi: 10.6023/cjoc201605044
Abstract:
A series of dihydroflavonol derivatives were synthesized by the reaction of 2'-hydroxyl chalcone derivatives with H2O2/(CH3CH2)2NH system in anhydrous tetrahydrofuran under low temperature. The influences of reaction temperature, re-action solvents, the kinds and proportion of alkaline additive and oxidants on this reaction were investigated, and the optimal reaction conditions were determined. This method has the advantages of simple operation, mild conditions and convenient post-treatment. Besides, all synthetic products were fully characterized by NMR spectra.
A series of dihydroflavonol derivatives were synthesized by the reaction of 2'-hydroxyl chalcone derivatives with H2O2/(CH3CH2)2NH system in anhydrous tetrahydrofuran under low temperature. The influences of reaction temperature, re-action solvents, the kinds and proportion of alkaline additive and oxidants on this reaction were investigated, and the optimal reaction conditions were determined. This method has the advantages of simple operation, mild conditions and convenient post-treatment. Besides, all synthetic products were fully characterized by NMR spectra.
2016, 36(11): 2757-2762
doi: 10.6023/cjoc201604056
Abstract:
Iodine catalyzed thiolation of various electron rich compounds using extensive source benzenesulfonyl chlorides as a sulfur source in presence of PPh3 as a reducing agent. The advantages of the present protocol include operational convenience, high efficiency and wide-application.
Iodine catalyzed thiolation of various electron rich compounds using extensive source benzenesulfonyl chlorides as a sulfur source in presence of PPh3 as a reducing agent. The advantages of the present protocol include operational convenience, high efficiency and wide-application.
2016, 36(11): 2763-2768
doi: 10.6023/cjoc201605013
Abstract:
As an important ubiquitin-like modifier protein in eukaryotic organisms, NEDD8 (neural precursor cell expressed developmentally down-regulated 8) is involved in regulating a series of important life processes in cells. Nowadays, the major method for obtaining NEDD8 is recombinant protein expression. However, the yield is relatively low and the recombined tag for purification needs to be removed in an extra step. In present work, NEDD8 protein was first synthesized in homogeneity by using high temperature assisted solid-phase peptide synthesis (SPPS) combining with the one-pot ligation-desulfurization strategy. This method lays the foundation for the study of NEDD8 modified proteins in future.
As an important ubiquitin-like modifier protein in eukaryotic organisms, NEDD8 (neural precursor cell expressed developmentally down-regulated 8) is involved in regulating a series of important life processes in cells. Nowadays, the major method for obtaining NEDD8 is recombinant protein expression. However, the yield is relatively low and the recombined tag for purification needs to be removed in an extra step. In present work, NEDD8 protein was first synthesized in homogeneity by using high temperature assisted solid-phase peptide synthesis (SPPS) combining with the one-pot ligation-desulfurization strategy. This method lays the foundation for the study of NEDD8 modified proteins in future.
