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2017 Volume 37 Issue 11
2017, 37(11): 2785-2799
doi: 10.6023/cjoc201708021
Abstract:
N-Heterocyclic rings are versatile structural units that widely dispersed in a variety of natural products, biological active species, and photoelectric materials. They are also useful building blocks in synthetic community. This review mainly focused on recent progress on gold-catalyzed intermolecular nitrene transfer reactions with alkynes. This strategy complements the toolbox for the synthesis of multisubstituted N-heterocyclic compounds. Mechanistically, activated by a suitable gold catalyst, the specific alkyne could react with a nitrene precursor, providing the final N-heterocyclic compounds in highly efficient manner.
N-Heterocyclic rings are versatile structural units that widely dispersed in a variety of natural products, biological active species, and photoelectric materials. They are also useful building blocks in synthetic community. This review mainly focused on recent progress on gold-catalyzed intermolecular nitrene transfer reactions with alkynes. This strategy complements the toolbox for the synthesis of multisubstituted N-heterocyclic compounds. Mechanistically, activated by a suitable gold catalyst, the specific alkyne could react with a nitrene precursor, providing the final N-heterocyclic compounds in highly efficient manner.
2017, 37(11): 2800-2817
doi: 10.6023/cjoc201604052
Abstract:
Deoxyribonucleic acid (DNA) is the genetic material determining the makeup of all living cells and many viruses. DNA has a self-replicating feature which consists of two polynucleotide chains in the form of a double helix. The synthesis of DNA-like double strand polymers has attracted much attention over recent years due to the development of self-assembly chemistry and organic synthesis technology. The synthesis of double strand polymers divided by the interaction including non-covalent bonding and covalent bonding between linker and backbone is sumarized. Poly-norbornene which could be performed as effcient backbone is also described. A series of isotactic double strand polymeric ladderphanes have been successfully acheived based on such poly-norbornene backbone.
Deoxyribonucleic acid (DNA) is the genetic material determining the makeup of all living cells and many viruses. DNA has a self-replicating feature which consists of two polynucleotide chains in the form of a double helix. The synthesis of DNA-like double strand polymers has attracted much attention over recent years due to the development of self-assembly chemistry and organic synthesis technology. The synthesis of double strand polymers divided by the interaction including non-covalent bonding and covalent bonding between linker and backbone is sumarized. Poly-norbornene which could be performed as effcient backbone is also described. A series of isotactic double strand polymeric ladderphanes have been successfully acheived based on such poly-norbornene backbone.
2017, 37(11): 2818-2840
doi: 10.6023/cjoc201705022
Abstract:
This review provides the brief history for the development and advances of ProTide strategies in the field of antiviral and anticancer pharmaceutical development. A summary is provided for the synthesis of nucleoside phosphoramidates, recent breakthroughs in the stereoselective assembly of chiral prodrugs and its application. This technology is extremely useful and has simplified innovative drug design of phosphorous-containing prodrugs. Simplifying such structural modification may create a new avenue of competition in the invention of new medicines from the parent drug.
This review provides the brief history for the development and advances of ProTide strategies in the field of antiviral and anticancer pharmaceutical development. A summary is provided for the synthesis of nucleoside phosphoramidates, recent breakthroughs in the stereoselective assembly of chiral prodrugs and its application. This technology is extremely useful and has simplified innovative drug design of phosphorous-containing prodrugs. Simplifying such structural modification may create a new avenue of competition in the invention of new medicines from the parent drug.
2017, 37(11): 2841-2849
doi: 10.6023/cjoc201706005
Abstract:
The formation of carbon-oxygen bonds is one of the hot topics in the field of organic synthesis methodology. Recently, the remarkable progress has been made in construction of carbon-oxygen bonds using tert-butyl hydroperoxide in radical reactions. The present protocol, which utilizes tert-butyl hydroperoxide as oxidant and oxygen source, provides a green and atom economy approach to ketones, esters and alcohols etc. This review will summarize the recent development in this area on the basis of different chemical bonds.
The formation of carbon-oxygen bonds is one of the hot topics in the field of organic synthesis methodology. Recently, the remarkable progress has been made in construction of carbon-oxygen bonds using tert-butyl hydroperoxide in radical reactions. The present protocol, which utilizes tert-butyl hydroperoxide as oxidant and oxygen source, provides a green and atom economy approach to ketones, esters and alcohols etc. This review will summarize the recent development in this area on the basis of different chemical bonds.
2017, 37(11): 2850-2858
doi: 10.6023/cjoc201703033
Abstract:
The reactions in which a new C-C bond is formed via a direct coupling of two C-H bonds are termed as cross dehydrogenative coupling (CDC). The coupling reactions would not need the pre-activation of the inert C-H bonds by any func-tional groups, featured with straightforwardness, atom-and step-economy and environmently benigness. Heterocycles are widely found in bioactive natural products and pharmaceuticals, designated as drug-like privileged scaffolds since they endowed diverse pharmacological effects. Preparation of these privileged structures by means of CDC confers distinctive advantages and enhances the discovery of lead compounds in medicinal chemistry. The application of CDC reactions in the synthesis of the heterocycles of pharmaceutical interest in recent years is summarized, focused on the construction of privileged scaffolds, such as indole, pyrrole, quinazoline, quinoxaline and the middle size and poly ring systems.
The reactions in which a new C-C bond is formed via a direct coupling of two C-H bonds are termed as cross dehydrogenative coupling (CDC). The coupling reactions would not need the pre-activation of the inert C-H bonds by any func-tional groups, featured with straightforwardness, atom-and step-economy and environmently benigness. Heterocycles are widely found in bioactive natural products and pharmaceuticals, designated as drug-like privileged scaffolds since they endowed diverse pharmacological effects. Preparation of these privileged structures by means of CDC confers distinctive advantages and enhances the discovery of lead compounds in medicinal chemistry. The application of CDC reactions in the synthesis of the heterocycles of pharmaceutical interest in recent years is summarized, focused on the construction of privileged scaffolds, such as indole, pyrrole, quinazoline, quinoxaline and the middle size and poly ring systems.
2017, 37(11): 2859-2872
doi: 10.6023/cjoc201705011
Abstract:
Organophosphine catalyst is a kind of strong nucleophilic Lewis base. It is widely used in the field of organic synthesis. An active and important zwitterion intermediate can be generated via nucleophilic addition of the tertiary phosphine to electron-deficient alkynoates or ynones and achieves further transformation, including isomerization, α-, β-, γ-addition reactions and [2+2], [3+2], [4+2] cycloaddition reactions. Varieties of pharmaceuticals, natural products and other bioactive moleculars could be efficiently synthesized through organophosphine-catalyzed cycloaddition reaction. The research of organ-ophosphine-catalyzed cycloaddition reaction of electron-deficient alkynoates or ynones has gained more attention. The recent development of organophosphine-catalyzed cycloaddition reaction of electron-deficient alkynoates or ynones is summarized.
Organophosphine catalyst is a kind of strong nucleophilic Lewis base. It is widely used in the field of organic synthesis. An active and important zwitterion intermediate can be generated via nucleophilic addition of the tertiary phosphine to electron-deficient alkynoates or ynones and achieves further transformation, including isomerization, α-, β-, γ-addition reactions and [2+2], [3+2], [4+2] cycloaddition reactions. Varieties of pharmaceuticals, natural products and other bioactive moleculars could be efficiently synthesized through organophosphine-catalyzed cycloaddition reaction. The research of organ-ophosphine-catalyzed cycloaddition reaction of electron-deficient alkynoates or ynones has gained more attention. The recent development of organophosphine-catalyzed cycloaddition reaction of electron-deficient alkynoates or ynones is summarized.
2017, 37(11): 2873-2882
doi: 10.6023/cjoc201705018
Abstract:
Carbon-halogen (C-X) bonds are amongst the most fundamental groups in organic synthesis, which are frequently and widely employed in the synthesis of numerous organic products. The generation of C-X bond, therefore, constitutes an issue of high interest. Herein, the research advances on the transition-metal-catalyzed C-X (X=Cl, Br, I) bond formation via direct C-H bond of aromatic compounds transformation by the use of N-halosuccinimide (NXS) is reviewed.
Carbon-halogen (C-X) bonds are amongst the most fundamental groups in organic synthesis, which are frequently and widely employed in the synthesis of numerous organic products. The generation of C-X bond, therefore, constitutes an issue of high interest. Herein, the research advances on the transition-metal-catalyzed C-X (X=Cl, Br, I) bond formation via direct C-H bond of aromatic compounds transformation by the use of N-halosuccinimide (NXS) is reviewed.
2017, 37(11): 2883-2894
doi: 10.6023/cjoc201705020
Abstract:
Spirobisnaphthalenes (spirodioxynaphthalenes) are one class of highly oxidized natural products in which two naphthalenes are connected by spiroketal or binaphthalene spiroether. Because of their novel and complex structures, multi-chiral centers and broad bioactivities, synthetic chemists paid a lot of attention to this type of compounds in recent years. The new research progresses of spirobisnaphthalene natural products after 2010 are reviewed based on the results in our laboratory, including 62 new chemical structures, total synthesis and modification, biosynthetic pathway, bioactivities and structure-activity relationships of spirobisnaphthalenes. The objective is to promote the creation of novel drugs and agrochemicals by lead discovery and modification of natural products in China.
Spirobisnaphthalenes (spirodioxynaphthalenes) are one class of highly oxidized natural products in which two naphthalenes are connected by spiroketal or binaphthalene spiroether. Because of their novel and complex structures, multi-chiral centers and broad bioactivities, synthetic chemists paid a lot of attention to this type of compounds in recent years. The new research progresses of spirobisnaphthalene natural products after 2010 are reviewed based on the results in our laboratory, including 62 new chemical structures, total synthesis and modification, biosynthetic pathway, bioactivities and structure-activity relationships of spirobisnaphthalenes. The objective is to promote the creation of novel drugs and agrochemicals by lead discovery and modification of natural products in China.
2017, 37(11): 2895-2904
doi: 10.6023/cjoc201705031
Abstract:
4-Hydroxyphenylpyruvate dioxygenase (HPPD), a target for green herbicide discovery, has recently attracted a large number of famous scientists attention owing to controlling efficacy of resistant weeds. The structures of HPPD, inhibitors binding sites, mode of action and their metabolites are summarized. The current commercial and developing pyrazole-containing herbicides of HPPD are analyzed. Based on combining theory and practical application, a direction to find or design a new inhibitor is also oriented.
4-Hydroxyphenylpyruvate dioxygenase (HPPD), a target for green herbicide discovery, has recently attracted a large number of famous scientists attention owing to controlling efficacy of resistant weeds. The structures of HPPD, inhibitors binding sites, mode of action and their metabolites are summarized. The current commercial and developing pyrazole-containing herbicides of HPPD are analyzed. Based on combining theory and practical application, a direction to find or design a new inhibitor is also oriented.
2017, 37(11): 2905-2910
doi: 10.6023/cjoc201706020
Abstract:
A mild, convenient, and economical approach for the construction of amides and lactams from ketoximes via Beckmann rearrangement by using a new type of Vilsmeier reagents generated in situ from thionyl chloride and 1-methyl-pyrrolidin-2-one was reported. Various amides and lactams bearing different substituents were obtained in good to excellent yields under mild conditions, and the gram scale reaction was achieved without the loss of the yield. Moreover, it can be used in the synthesis of 2-methylbenzoxazole from 1-(2-hydroxyphenyl)ethanone oxime.
A mild, convenient, and economical approach for the construction of amides and lactams from ketoximes via Beckmann rearrangement by using a new type of Vilsmeier reagents generated in situ from thionyl chloride and 1-methyl-pyrrolidin-2-one was reported. Various amides and lactams bearing different substituents were obtained in good to excellent yields under mild conditions, and the gram scale reaction was achieved without the loss of the yield. Moreover, it can be used in the synthesis of 2-methylbenzoxazole from 1-(2-hydroxyphenyl)ethanone oxime.
2017, 37(11): 2911-2918
doi: 10.6023/cjoc201705016
Abstract:
[1+1] Schiff base macrocycle 3 has been synthesized from the reaction of precursors N, N'-bis(3-aminophenyl)-pyridine-2, 6-dicarboxamide (1) with 5, 5-dimethyl-1, 9-diformyldipyrromethane (2), and furthermore the macrocycle 3 was reduced to the corresponding saturated macrocycle 4. The two macrocycles were characterized by 1H NMR, FT-IR, FABMS spectroscopies and elemental analysis, and the crystal structure of 4 was determined by X-ray diffraction analysis. Properties of the two macrocycles hydrogen-bonding interactions with AcO- were investigated using UV-Vis, 1H NMR, the isothermal titration calorimeter (ITC), as well as density functional theory (DFT) calculations. The stoichiometric ratio, binding constant (K) and the thermodynamic parameters (ΔrHm, ΔrSm and ΔrGm) of binding interactions were obtained. The results demonstrate that the macrocycle 3 binds AcO- with a 1:1 binding stoichiometry (Ka≈105 L·mol-1), and the more flexible macrocyclic receptor 4 binds AcO- with a 1:2 binding stoichiometry (Ka1≈103 L·mol-1, Ka2≈105 L·mol-1).
[1+1] Schiff base macrocycle 3 has been synthesized from the reaction of precursors N, N'-bis(3-aminophenyl)-pyridine-2, 6-dicarboxamide (1) with 5, 5-dimethyl-1, 9-diformyldipyrromethane (2), and furthermore the macrocycle 3 was reduced to the corresponding saturated macrocycle 4. The two macrocycles were characterized by 1H NMR, FT-IR, FABMS spectroscopies and elemental analysis, and the crystal structure of 4 was determined by X-ray diffraction analysis. Properties of the two macrocycles hydrogen-bonding interactions with AcO- were investigated using UV-Vis, 1H NMR, the isothermal titration calorimeter (ITC), as well as density functional theory (DFT) calculations. The stoichiometric ratio, binding constant (K) and the thermodynamic parameters (ΔrHm, ΔrSm and ΔrGm) of binding interactions were obtained. The results demonstrate that the macrocycle 3 binds AcO- with a 1:1 binding stoichiometry (Ka≈105 L·mol-1), and the more flexible macrocyclic receptor 4 binds AcO- with a 1:2 binding stoichiometry (Ka1≈103 L·mol-1, Ka2≈105 L·mol-1).
2017, 37(11): 2919-2928
doi: 10.6023/cjoc201706035
Abstract:
A robust chiral N-heterocyclic carbene precursor based on[2.2]paracyclophane was designed and synthesized for a highly enantioselective metal-free catalytic boration. Enantioselective 1, 4-addition of a commercially available bis(pinacolato)-diboron (B2(pin)2) to chalcones was achieved by using the new bifunctional chiral carbene as catalyst, affording the corresponding products in up to 99% yield and 97% enantiomeric excess. Moreover, it was found that water used as the additive plays a key role in the carbene-catalyzed enantioselective boration.
A robust chiral N-heterocyclic carbene precursor based on[2.2]paracyclophane was designed and synthesized for a highly enantioselective metal-free catalytic boration. Enantioselective 1, 4-addition of a commercially available bis(pinacolato)-diboron (B2(pin)2) to chalcones was achieved by using the new bifunctional chiral carbene as catalyst, affording the corresponding products in up to 99% yield and 97% enantiomeric excess. Moreover, it was found that water used as the additive plays a key role in the carbene-catalyzed enantioselective boration.
2017, 37(11): 2929-2939
doi: 10.6023/cjoc201706036
Abstract:
A natural trisaccharide α-D-rhamnopyanosyl-(1→3)-α-L-fucopyranosyl-(1→4)-β-D-xylopyranoside was synthesized from xylose glycoside donor, fucose glycoside donor and rhamnopyanosyl glycoside donor using α-D-xylopyranoside, β-L-fucopyranoside and α-D-rhamnopyranoside as the raw material respectively. This trisaccharide is a repeating-structure of the cell wall of the Azospirillum brasilense type strain Sp7. In the critical glycosylation reaction between rhamnopyanosyl glycoside donor and disaccharide receptor, full protected trisaccharide was regioselectivity builded. Streamlined the synthesis steps and the total yield of trisaccharide is 10% base on β-L-fucopyranoside. This route is suitable for mass preparation of target products. Preliminary determination of plant growth regulating activity of germination bed in sand culture showed that at 100 mg/L concen-tration, the trisaccharide raised the rate of emergence, the plant height and the leaf area by 11.0%, 13.1% and 87.8%, respectively. It was preliminarily concluded that this trisaccharide had certain plant growth regulating activity.
A natural trisaccharide α-D-rhamnopyanosyl-(1→3)-α-L-fucopyranosyl-(1→4)-β-D-xylopyranoside was synthesized from xylose glycoside donor, fucose glycoside donor and rhamnopyanosyl glycoside donor using α-D-xylopyranoside, β-L-fucopyranoside and α-D-rhamnopyranoside as the raw material respectively. This trisaccharide is a repeating-structure of the cell wall of the Azospirillum brasilense type strain Sp7. In the critical glycosylation reaction between rhamnopyanosyl glycoside donor and disaccharide receptor, full protected trisaccharide was regioselectivity builded. Streamlined the synthesis steps and the total yield of trisaccharide is 10% base on β-L-fucopyranoside. This route is suitable for mass preparation of target products. Preliminary determination of plant growth regulating activity of germination bed in sand culture showed that at 100 mg/L concen-tration, the trisaccharide raised the rate of emergence, the plant height and the leaf area by 11.0%, 13.1% and 87.8%, respectively. It was preliminarily concluded that this trisaccharide had certain plant growth regulating activity.
2017, 37(11): 2940-2947
doi: 10.6023/cjoc201704045
Abstract:
Four N-phenylcarbazole sensitizers were designed and synthesized with N-phenylcarbazole as the electron donor, benzothiadiazole as the auxiliary acceptor, thiophene or benzene as π bridge, cyanoacetic acid or rhodanine acetic acid as the an-choring acceptor. The spectral properties and photovoltaic performance of the sensitizers were investigated. Though with short maximum absorption wavelength and low molar extinction coefficient, dyes with cyanoacetic acid acceptor show higher electron injection efficiency than dyes with rhodanine acetic acid acceptor, and hence obtain superior photocurrent and photovoltage. Dyes with benzene bridge exhibit higher photocurrent and photovoltage than dyes with thiophene bridge. Therefore, among four sensitizers, dye with benzene bridge and cyanoacetic acid acceptor obtains better photoelectric conversion efficiency of 5.28% (JSC=9.14 mA/cm2, VOC=0.74 V, FF=0.78).
Four N-phenylcarbazole sensitizers were designed and synthesized with N-phenylcarbazole as the electron donor, benzothiadiazole as the auxiliary acceptor, thiophene or benzene as π bridge, cyanoacetic acid or rhodanine acetic acid as the an-choring acceptor. The spectral properties and photovoltaic performance of the sensitizers were investigated. Though with short maximum absorption wavelength and low molar extinction coefficient, dyes with cyanoacetic acid acceptor show higher electron injection efficiency than dyes with rhodanine acetic acid acceptor, and hence obtain superior photocurrent and photovoltage. Dyes with benzene bridge exhibit higher photocurrent and photovoltage than dyes with thiophene bridge. Therefore, among four sensitizers, dye with benzene bridge and cyanoacetic acid acceptor obtains better photoelectric conversion efficiency of 5.28% (JSC=9.14 mA/cm2, VOC=0.74 V, FF=0.78).
2017, 37(11): 2948-2955
doi: 10.6023/cjoc201705027
Abstract:
A Pd-pyridine N-heterocyclic carbene complex (NHC)PdCl2(Py) has been synthesized through two steps and successfully applied as an effective catalyst for the Suzuki coupling reaction, Heck coupling reaction and Sonogashira coupling reaction. The catalyst demonstrates excellent catalytic activity in Suzuki coupling reaction and Sonogashira coupling reaction with a catalyst loading of 0.1 mol% and 1 mol% in Heck coupling reaction.
A Pd-pyridine N-heterocyclic carbene complex (NHC)PdCl2(Py) has been synthesized through two steps and successfully applied as an effective catalyst for the Suzuki coupling reaction, Heck coupling reaction and Sonogashira coupling reaction. The catalyst demonstrates excellent catalytic activity in Suzuki coupling reaction and Sonogashira coupling reaction with a catalyst loading of 0.1 mol% and 1 mol% in Heck coupling reaction.
2017, 37(11): 2956-2961
doi: 10.6023/cjoc201706016
Abstract:
Efficient and unsupported protocols were developed for PdCl2-catalyzed Suzuki-Miyaura and Mizoroki-Heck reactions using water/ionic liquid systems to afford the cross-coupling products with excellent yields. It is noteworthy that the PdCl2/K2CO3/water/ionic liquid systems can be recovered and used for 3~5 cycles directly. The results suggest that the unsupported and recyclable systems can be extended to the other realm of C-C bond formation.
Efficient and unsupported protocols were developed for PdCl2-catalyzed Suzuki-Miyaura and Mizoroki-Heck reactions using water/ionic liquid systems to afford the cross-coupling products with excellent yields. It is noteworthy that the PdCl2/K2CO3/water/ionic liquid systems can be recovered and used for 3~5 cycles directly. The results suggest that the unsupported and recyclable systems can be extended to the other realm of C-C bond formation.
2017, 37(11): 2962-2971
doi: 10.6023/cjoc201703015
Abstract:
Vicinal bromoamine derivative belongs to an important class of difunctionalization compounds. New synthetic method and new vicinal bromoamine derivatives are eagerly desired. Thus, a new one-pot protocol for the synthesis of vicinal bromoamines from β, β-dicyanostyrene derivatives/amides/N-bromo-succinimide was developed. In the presence of anhydrous K2CO3, β, β-dicyanostyrenes reacted smoothly with amides and N-bromo-succinimide (NBS) to generate the vicinal bromoamine compounds in good to excellent yield (up to 93% yield) at room temperature without the protection of inert gas in CH2Cl2. 13 different structural β, β-dicyanostyrene derivatives reacted with 7 different structural amides (acrylamide, acetamide, valeramide, isobutyramide, benzamide, 4-nitrobenzamide, ethylurethanm) and NBS have been investigated in this work. The results indicated that the method is not only widely subjected to β, β-dicyanostyrene, but also suitable for the different type of amide. The structures of all the products were confirmed by their nuclear magnetic resonance spectroscopy (NMR), infrared spectra (IR) and high reso-lution mass spectrometry (HRMS), and the possible reaction mechanism was proposed.
Vicinal bromoamine derivative belongs to an important class of difunctionalization compounds. New synthetic method and new vicinal bromoamine derivatives are eagerly desired. Thus, a new one-pot protocol for the synthesis of vicinal bromoamines from β, β-dicyanostyrene derivatives/amides/N-bromo-succinimide was developed. In the presence of anhydrous K2CO3, β, β-dicyanostyrenes reacted smoothly with amides and N-bromo-succinimide (NBS) to generate the vicinal bromoamine compounds in good to excellent yield (up to 93% yield) at room temperature without the protection of inert gas in CH2Cl2. 13 different structural β, β-dicyanostyrene derivatives reacted with 7 different structural amides (acrylamide, acetamide, valeramide, isobutyramide, benzamide, 4-nitrobenzamide, ethylurethanm) and NBS have been investigated in this work. The results indicated that the method is not only widely subjected to β, β-dicyanostyrene, but also suitable for the different type of amide. The structures of all the products were confirmed by their nuclear magnetic resonance spectroscopy (NMR), infrared spectra (IR) and high reso-lution mass spectrometry (HRMS), and the possible reaction mechanism was proposed.
2017, 37(11): 2972-2977
doi: 10.6023/cjoc201705038
Abstract:
A concise and efficiently route for the synthesis of isoquinolinones via one-step reaction of nitro substituted methyl 2-fluorobenzoate 1 and heterocyclic ketone aminals (HKAs, 2) in 1, 4-dioxane catalyzed by Cs2CO3 under reflux conditions has been developed. Isoquinolinones 3 were obtained by one-step strategy. This protocol possesses some advantages including readily available starting materials, simple operation and concise synthetic route and so on.
A concise and efficiently route for the synthesis of isoquinolinones via one-step reaction of nitro substituted methyl 2-fluorobenzoate 1 and heterocyclic ketone aminals (HKAs, 2) in 1, 4-dioxane catalyzed by Cs2CO3 under reflux conditions has been developed. Isoquinolinones 3 were obtained by one-step strategy. This protocol possesses some advantages including readily available starting materials, simple operation and concise synthetic route and so on.
2017, 37(11): 2978-2984
doi: 10.6023/cjoc201706029
Abstract:
Acetyl-CoA carboxylase (ACCase, EC 6.4.1.2) was one of important herbicidal targets. However, the number of resistant weeds targeting to ACCase had risen to the third place among all of herbicidal targets. Therefore, it is of great importance to design new ACCase inhibitors. Herein, based on the crystal structures, aryloxyphenoxypropanotes (APP)-site and cyclohexanedioneoximes (CHD)-site were used to constructing APP+CHD-site, and then thirteen compounds were designed and synthesized. All the newly prepared compounds were characterized by 1H NMR, 13C NMR and HRMS. The molecular docking showed that 2-((4-(2, 4-dichlorophenoxy)phenoxy)methyl)-5-(2-(ethylthio)propyl)cyclohexane-1, 3-dione (10a) could occupy not only APP-site, but also CHD-site. In addition, based on the herbicidal activity, some compounds showed some inhibition rate upon tested weeds. Most importantly, 5-(2-(ethylthio)propyl)-2-((4-phenoxyphenoxy)methyl)cyclohexane-1, 3-dione (10b) showed a wide range of herbicidal spectrum, which could be used to inhibit not only poaceae weeds, but also broadleaf weeds. All these results indicated that this type of compounds worth of the further investigation.
Acetyl-CoA carboxylase (ACCase, EC 6.4.1.2) was one of important herbicidal targets. However, the number of resistant weeds targeting to ACCase had risen to the third place among all of herbicidal targets. Therefore, it is of great importance to design new ACCase inhibitors. Herein, based on the crystal structures, aryloxyphenoxypropanotes (APP)-site and cyclohexanedioneoximes (CHD)-site were used to constructing APP+CHD-site, and then thirteen compounds were designed and synthesized. All the newly prepared compounds were characterized by 1H NMR, 13C NMR and HRMS. The molecular docking showed that 2-((4-(2, 4-dichlorophenoxy)phenoxy)methyl)-5-(2-(ethylthio)propyl)cyclohexane-1, 3-dione (10a) could occupy not only APP-site, but also CHD-site. In addition, based on the herbicidal activity, some compounds showed some inhibition rate upon tested weeds. Most importantly, 5-(2-(ethylthio)propyl)-2-((4-phenoxyphenoxy)methyl)cyclohexane-1, 3-dione (10b) showed a wide range of herbicidal spectrum, which could be used to inhibit not only poaceae weeds, but also broadleaf weeds. All these results indicated that this type of compounds worth of the further investigation.
2017, 37(11): 2985-2992
doi: 10.6023/cjoc201703050
Abstract:
An one-pot reaction of trifluoroacetaldehyde methyl hemiacetal or trifluoroketones, acylhydrazines and ethyl 2-(bromomethyl)acrylate promoted by indium powder has been investigated and a series of α-methylene-γ-trifluoromethyl-γ-lactams were obtained with high yieds. The features of this process include readily available starting materials as trifluoromethyl source, mild conditions and easy operation. The reaction provides a new method for the snythesis of trifluoromethylated α-methylene-γ-lactams.
An one-pot reaction of trifluoroacetaldehyde methyl hemiacetal or trifluoroketones, acylhydrazines and ethyl 2-(bromomethyl)acrylate promoted by indium powder has been investigated and a series of α-methylene-γ-trifluoromethyl-γ-lactams were obtained with high yieds. The features of this process include readily available starting materials as trifluoromethyl source, mild conditions and easy operation. The reaction provides a new method for the snythesis of trifluoromethylated α-methylene-γ-lactams.
2017, 37(11): 2993-2999
doi: 10.6023/cjoc201704037
Abstract:
α-Hydroxyl amides are important skeleton and valuable intermediates that present in many natural products, pharmaceutical active compounds, and organic functional materials. The main methods for synthesis of α-hydroxyl amides are either through amidation of α-hydroxyl acids, or by reduction of α-keto amides. Herein, a convenient potassium hydroxide/dimethyl sulfoxide promoted aerobic oxidation reaction to prepare N-substituted α-hydroxyl phenylacetamides is reported in good to high yields. 21 corresponding products were obtained and characterized by 1H NMR, 13C NMR and HRMS. The molecular structure of 2-(2-bromophenyl)-2-hydroxy-N-(p-tolyl)acetamide (2a) was confirmed by using single-crystal X-ray analyses.
α-Hydroxyl amides are important skeleton and valuable intermediates that present in many natural products, pharmaceutical active compounds, and organic functional materials. The main methods for synthesis of α-hydroxyl amides are either through amidation of α-hydroxyl acids, or by reduction of α-keto amides. Herein, a convenient potassium hydroxide/dimethyl sulfoxide promoted aerobic oxidation reaction to prepare N-substituted α-hydroxyl phenylacetamides is reported in good to high yields. 21 corresponding products were obtained and characterized by 1H NMR, 13C NMR and HRMS. The molecular structure of 2-(2-bromophenyl)-2-hydroxy-N-(p-tolyl)acetamide (2a) was confirmed by using single-crystal X-ray analyses.
2017, 37(11): 3000-3005
doi: 10.6023/cjoc201705044
Abstract:
Two kinds of different spacer biquaternary ammonium salts N1, N3-dibenzyl-2-hydroxy-N1, N1, N3, N3-tetra-methylpropane-1, 3-diaminium dichloride (Q1) and N1, N6-dibenzyl-N1, N1, N6, N6-tetramethylhexane-1, 6-diaminium dibromide (Q2) were prepared to modify montmorillonite (MMT). Copper was loaded on the modified MMT by the impregnation reduction method to form two kinds of catalytic materials Cu-Q1-MMT and Cu-Q2-MMT. They were applied to the coupling of aryl halides and aqueous ammonia. It was found that they were high active and selective catalysts for the coupling of aryl halides with aqueous ammonia under mild conditions without inert gas protection. Compared with Cu-Q1-MMT, Cu-Q2-MMT showed a higher catalytic activity. In addition, it could be separated easily and reused for 17 consecutive runs without significant loss in catalytic activity.
Two kinds of different spacer biquaternary ammonium salts N1, N3-dibenzyl-2-hydroxy-N1, N1, N3, N3-tetra-methylpropane-1, 3-diaminium dichloride (Q1) and N1, N6-dibenzyl-N1, N1, N6, N6-tetramethylhexane-1, 6-diaminium dibromide (Q2) were prepared to modify montmorillonite (MMT). Copper was loaded on the modified MMT by the impregnation reduction method to form two kinds of catalytic materials Cu-Q1-MMT and Cu-Q2-MMT. They were applied to the coupling of aryl halides and aqueous ammonia. It was found that they were high active and selective catalysts for the coupling of aryl halides with aqueous ammonia under mild conditions without inert gas protection. Compared with Cu-Q1-MMT, Cu-Q2-MMT showed a higher catalytic activity. In addition, it could be separated easily and reused for 17 consecutive runs without significant loss in catalytic activity.
2017, 37(11): 3006-3012
doi: 10.6023/cjoc201707022
Abstract:
In order to find new pyrazole derivatives with potent biological activities, a series of novel pyrazole amides containing heptafluoroisopropyl moiety were prepared according to the method of active substructure combination. Their structures were characterized by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data showed that some target compounds displayed good insecticidal activities. At the concentration of 500 μg/mL, eleven compounds had insecticidal activity against Oriental armyworm of 60%~100%. When the concentration was reduced to 100 μg/mL, three compounds showed insecticidal activity against Oriental armyworm of 60%~70%, better than that of the control tolfenpyrad.
In order to find new pyrazole derivatives with potent biological activities, a series of novel pyrazole amides containing heptafluoroisopropyl moiety were prepared according to the method of active substructure combination. Their structures were characterized by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data showed that some target compounds displayed good insecticidal activities. At the concentration of 500 μg/mL, eleven compounds had insecticidal activity against Oriental armyworm of 60%~100%. When the concentration was reduced to 100 μg/mL, three compounds showed insecticidal activity against Oriental armyworm of 60%~70%, better than that of the control tolfenpyrad.
2017, 37(11): 3013-3018
doi: 10.6023/cjoc201704053
Abstract:
Diphenyl chlorophosphate-promoted condensation reaction of aromatic aldehydes and sulfones, proceeding at room temperature, could been applied to synthesize unsymmetrical aromatic acetylenes. It was found that functional groups on aromatic ring of aldehydes and sulfones had little effect on the reaction. A series of unsymmetrical diphenyl, thienyl, pyridyl, coumarin and diphenylphosphoryl aromatic acetylenes were prepared by the reaction. Based on the molecular structure, the reason why this reaction could proceed at room temperature is explained The reaction showed some outstanding features including simple operation, wide functional group tolerance, high yields and mild reaction conditions.
Diphenyl chlorophosphate-promoted condensation reaction of aromatic aldehydes and sulfones, proceeding at room temperature, could been applied to synthesize unsymmetrical aromatic acetylenes. It was found that functional groups on aromatic ring of aldehydes and sulfones had little effect on the reaction. A series of unsymmetrical diphenyl, thienyl, pyridyl, coumarin and diphenylphosphoryl aromatic acetylenes were prepared by the reaction. Based on the molecular structure, the reason why this reaction could proceed at room temperature is explained The reaction showed some outstanding features including simple operation, wide functional group tolerance, high yields and mild reaction conditions.
2017, 37(11): 3019-3023
doi: 10.6023/cjoc201706031
Abstract:
In our phytochemical investigations on the 80% EtOH extract of the rhizomes of Atractylodes lancea, two new compounds named (10R, 11R, 12R)-tridecane-2E, 8E-diene-4, 6-diyne-1, 10, 11, 12, 13-pentol-10-O-β-D-glucopyranoside (1) and isoscopoletin 6-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside (2) were isolated using various column chromatographic methods. Their planar structures were elucidated by means of spectroscopic and spectrometric analyses (UV, IR, 1D and 2D NMR, and HR-ESIMS). The relative configurational assignment of 1 was deduced by visualized Newman projections in association with the 1D NOESY spectra, whereas its absolute configuration was established by comparison of experimental electronic circular dichroism (ECD) spectra with known compounds. These results will benefit subsequent stereochemical studies of those open-chain polyhydric alcohols. Compounds 1 and 2 showed weak inhibitory effects on α-glucosidases and protein tyrosine phosphates 1B (PTP1B) at a concentration of 10 μmol·L-1.
In our phytochemical investigations on the 80% EtOH extract of the rhizomes of Atractylodes lancea, two new compounds named (10R, 11R, 12R)-tridecane-2E, 8E-diene-4, 6-diyne-1, 10, 11, 12, 13-pentol-10-O-β-D-glucopyranoside (1) and isoscopoletin 6-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside (2) were isolated using various column chromatographic methods. Their planar structures were elucidated by means of spectroscopic and spectrometric analyses (UV, IR, 1D and 2D NMR, and HR-ESIMS). The relative configurational assignment of 1 was deduced by visualized Newman projections in association with the 1D NOESY spectra, whereas its absolute configuration was established by comparison of experimental electronic circular dichroism (ECD) spectra with known compounds. These results will benefit subsequent stereochemical studies of those open-chain polyhydric alcohols. Compounds 1 and 2 showed weak inhibitory effects on α-glucosidases and protein tyrosine phosphates 1B (PTP1B) at a concentration of 10 μmol·L-1.
2017, 37(11): 3024-3030
doi: 10.6023/cjoc201702024
Abstract:
A bifunctional fluorescent probe 1, 1'-(5, 5'-(6, 6'-dihydroxy-5, 5'-dimethoxybiphenyl-3, 3'-diyl)bis(3-(2-hydroxy-phenyl)-1H-pyrazole-5, 1(4H, 5H)-diyl))diethanone (C1) based on bispyrazoline was designed and synthesized. The structure of C1 was confirmed by 1H NMR, 13C NMR, MS and elemental analysis. The spectroscopic behavior toward metal ions has been investigated by the absorption and fluorescence methods. It exhibited high sensitivity and selectivity for detecting Cu2+ and Zn2+ over other commonly coexistent metal ions in 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) buffer solution[V(MeOH):V(H2O)=1:1, 20 mol·L-1, pH=7.4] and it has the capability to differentiate target ions with different flu-orescence.
A bifunctional fluorescent probe 1, 1'-(5, 5'-(6, 6'-dihydroxy-5, 5'-dimethoxybiphenyl-3, 3'-diyl)bis(3-(2-hydroxy-phenyl)-1H-pyrazole-5, 1(4H, 5H)-diyl))diethanone (C1) based on bispyrazoline was designed and synthesized. The structure of C1 was confirmed by 1H NMR, 13C NMR, MS and elemental analysis. The spectroscopic behavior toward metal ions has been investigated by the absorption and fluorescence methods. It exhibited high sensitivity and selectivity for detecting Cu2+ and Zn2+ over other commonly coexistent metal ions in 4-(2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES) buffer solution[V(MeOH):V(H2O)=1:1, 20 mol·L-1, pH=7.4] and it has the capability to differentiate target ions with different flu-orescence.
2017, 37(11): 3031-3036
doi: 10.6023/cjoc201705029
Abstract:
Using seedvax as leading compound, seventeen new seedvax analogues N-substituted-4-methyl-5-aminothia-zole-2-benzamides were designed and synthesized. The structures of the target compounds were characterized by 1H NMR, 13C NMR, HRMS and IR spectral analyses. The preliminary bioassay results of fungicidal activities (FA) in vitro showed that most of the target compounds displayed higher activities than seedvax. Among them, the FA against Alternaria solani of one compound is 2.6 times of seedvax, the FA of 6 compounds against cucumber Fusarium wilt are more than 2 times of that of seedvax; the FA of 16 compounds against Colletotrichun orbiculare and Fusarium fujikuroi were higher than that of positive control. Especially, the FA against Colletotrichun orbiculare of seven compounds are more than twice of seedvax.
Using seedvax as leading compound, seventeen new seedvax analogues N-substituted-4-methyl-5-aminothia-zole-2-benzamides were designed and synthesized. The structures of the target compounds were characterized by 1H NMR, 13C NMR, HRMS and IR spectral analyses. The preliminary bioassay results of fungicidal activities (FA) in vitro showed that most of the target compounds displayed higher activities than seedvax. Among them, the FA against Alternaria solani of one compound is 2.6 times of seedvax, the FA of 6 compounds against cucumber Fusarium wilt are more than 2 times of that of seedvax; the FA of 16 compounds against Colletotrichun orbiculare and Fusarium fujikuroi were higher than that of positive control. Especially, the FA against Colletotrichun orbiculare of seven compounds are more than twice of seedvax.
