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2020 Volume 40 Issue 12
2020, 40(12): 3991-4014
doi: 10.6023/cjoc202006024
Abstract:
The formation of chiral amine intermediates with chiral tert-butanesulfinamide and their applications in asymmetric natural product synthesis in recent years are summarized. tert-Butanesulfinamide has attracted wide attention from chemists because it is stable, commercially available with reasonable price, ease to use, and usually induces high diastereoselectivity in the reactions involved. This review is divided into two sections, including the addition of nucleophiles to tert-butanesulfinyl imide and the addition of tert-butanesulfinyl metal enamine to electrophiles.
The formation of chiral amine intermediates with chiral tert-butanesulfinamide and their applications in asymmetric natural product synthesis in recent years are summarized. tert-Butanesulfinamide has attracted wide attention from chemists because it is stable, commercially available with reasonable price, ease to use, and usually induces high diastereoselectivity in the reactions involved. This review is divided into two sections, including the addition of nucleophiles to tert-butanesulfinyl imide and the addition of tert-butanesulfinyl metal enamine to electrophiles.
2020, 40(12): 4015-4030
doi: 10.6023/cjoc202008042
Abstract:
N-Substituted-1, 2, 3-triazoles are an important class of nitrogen-containing hetrocyclic compounds, which exhibited wide applications in various fields such as medicinal chemistry, synthetic chemistry and materials. Therefore, their synthetic methods have attracted great attention of chemists. Herein, the recent research progress in the synthesis of N-substituted-1, 2, 3-triazoles is summarized. The synthetic routes and reaction mechanisms from raw materials such as azide compounds, diazo compounds, TsNHNH2, hydrazones and NH-1, 2, 3-triazoles are introduced and reviewed, respectively. Finally, the future development of this field is also prospected.
N-Substituted-1, 2, 3-triazoles are an important class of nitrogen-containing hetrocyclic compounds, which exhibited wide applications in various fields such as medicinal chemistry, synthetic chemistry and materials. Therefore, their synthetic methods have attracted great attention of chemists. Herein, the recent research progress in the synthesis of N-substituted-1, 2, 3-triazoles is summarized. The synthetic routes and reaction mechanisms from raw materials such as azide compounds, diazo compounds, TsNHNH2, hydrazones and NH-1, 2, 3-triazoles are introduced and reviewed, respectively. Finally, the future development of this field is also prospected.
2020, 40(12): 4031-4045
doi: 10.6023/cjoc202005023
Abstract:
Donor-acceptor-donor (D-A-D) type polycyclic aromatic hydrocarbon and its derivatives have been widely used in the design of photovoltaic materials and have made great breakthrough in recent years, due to their advantages of unique large planar structure, high charge mobility, excellent light absorption performance, thermal and light stability. The latest research progress of small-molecule photovoltaic materials based on D-A-D type polycyclic aromatic hydrocarbons is reviewed. The relationships between photovoltaic properties and the molecular structures are analyzed systematically.
Donor-acceptor-donor (D-A-D) type polycyclic aromatic hydrocarbon and its derivatives have been widely used in the design of photovoltaic materials and have made great breakthrough in recent years, due to their advantages of unique large planar structure, high charge mobility, excellent light absorption performance, thermal and light stability. The latest research progress of small-molecule photovoltaic materials based on D-A-D type polycyclic aromatic hydrocarbons is reviewed. The relationships between photovoltaic properties and the molecular structures are analyzed systematically.
2020, 40(12): 4046-4059
doi: 10.6023/cjoc202005063
Abstract:
Organic fluorescent polymers have unique characteristics of fluorescent signal amplification and good optical properties, and can detect specific analytical species. Their sensing performance can be further improved through reasonable modification of their side chains. Nowadays, the organic fluorescent polymers are mainly prepared by metal coupling reactions, and there are also some syntheses involving in addition polymerization and condensation reactions. Taking the fluorescent source of these polymers as the main line, the research progress of the fluorescent organic polymers in the sensor field in recent years is systematically reviewed from the perspective of the type of reaction, especially their design and synthesis, sensing application, detection mechanism are summarized. In the future, it is still to be further investigated to design and synthesize novel multifunctional organic polymer fluorescence sensors as the key development direction.
Organic fluorescent polymers have unique characteristics of fluorescent signal amplification and good optical properties, and can detect specific analytical species. Their sensing performance can be further improved through reasonable modification of their side chains. Nowadays, the organic fluorescent polymers are mainly prepared by metal coupling reactions, and there are also some syntheses involving in addition polymerization and condensation reactions. Taking the fluorescent source of these polymers as the main line, the research progress of the fluorescent organic polymers in the sensor field in recent years is systematically reviewed from the perspective of the type of reaction, especially their design and synthesis, sensing application, detection mechanism are summarized. In the future, it is still to be further investigated to design and synthesize novel multifunctional organic polymer fluorescence sensors as the key development direction.
2020, 40(12): 4060-4070
doi: 10.6023/cjoc202005039
Abstract:
Sulfur-containing heterocyclic compounds such as thiazole, thiophene, thiopyrone, widely exist in numerous natural products and biologically active molecules. Developing of effective strategies for the formation of sulfur-containing heterocycles has become a popular research hotspot. Meanwhile, the free-radical cascade reaction of unsaturated bonds in the synthesis of heterocycle has always been an important branch of synthetic chemistry, and the achieved progresses in recent years have also demonstrated its huge potential. Researchers found that sulfur atom could act as radical acceptors to build a C-S bond, and established a series of free radical reactions through this strategy. Among them, the radical cascade reactions of anisole derivatives have been gradually developed into an important synthetic tool toward sulfur-containing heterocycles. The recent advances in the field of radical-initiated reactions of anisoles for the construction of sulfur-containing heterocycles, in which sulfur atoms play as radical acceptors, are summarized. In addition, the reaction design, mechanism and applicability of sulfur-containing heterocyclic compounds via radical cyclization towards the synthesis of complex molecules are also covered.
Sulfur-containing heterocyclic compounds such as thiazole, thiophene, thiopyrone, widely exist in numerous natural products and biologically active molecules. Developing of effective strategies for the formation of sulfur-containing heterocycles has become a popular research hotspot. Meanwhile, the free-radical cascade reaction of unsaturated bonds in the synthesis of heterocycle has always been an important branch of synthetic chemistry, and the achieved progresses in recent years have also demonstrated its huge potential. Researchers found that sulfur atom could act as radical acceptors to build a C-S bond, and established a series of free radical reactions through this strategy. Among them, the radical cascade reactions of anisole derivatives have been gradually developed into an important synthetic tool toward sulfur-containing heterocycles. The recent advances in the field of radical-initiated reactions of anisoles for the construction of sulfur-containing heterocycles, in which sulfur atoms play as radical acceptors, are summarized. In addition, the reaction design, mechanism and applicability of sulfur-containing heterocyclic compounds via radical cyclization towards the synthesis of complex molecules are also covered.
2020, 40(12): 4071-4086
doi: 10.6023/cjoc202004047
Abstract:
Owning to their low cost and readily available, quinoline N-oxides are widely used in organic synthesis. The functionalization reactions of C(2) and C(8) position of quinoline N-oxides and the reaction mechanisms of these reactions are summaried. It will be helpful for the reaction of quinoline N-oxide in the future.
Owning to their low cost and readily available, quinoline N-oxides are widely used in organic synthesis. The functionalization reactions of C(2) and C(8) position of quinoline N-oxides and the reaction mechanisms of these reactions are summaried. It will be helpful for the reaction of quinoline N-oxide in the future.
2020, 40(12): 4087-4100
doi: 10.6023/cjoc202005047
Abstract:
Arylphosphine and aryl sulfur compounds have been widely used in organic synthesis, functional materials and pharmaceutical chemistry. Thus, the development of green, mild and highly efficient methodologies for P- and S-arylation is of great importance. Recently, the reactions involving arynes provided a novel approach to the arylation of organophosphorus and organosulfur compounds. These reactions can be performed in the absence of transition metal catalysts under mild conditions with broad scope. The recent progress in P- and S-arylation reactions with arynes is introduced on the basis of different reaction types.
Arylphosphine and aryl sulfur compounds have been widely used in organic synthesis, functional materials and pharmaceutical chemistry. Thus, the development of green, mild and highly efficient methodologies for P- and S-arylation is of great importance. Recently, the reactions involving arynes provided a novel approach to the arylation of organophosphorus and organosulfur compounds. These reactions can be performed in the absence of transition metal catalysts under mild conditions with broad scope. The recent progress in P- and S-arylation reactions with arynes is introduced on the basis of different reaction types.
2020, 40(12): 4101-4121
doi: 10.6023/cjoc202004049
Abstract:
The recent advances on the structural modifications and chiral applications of Brucine are reviewed. Brucine is a naturally occuring molecule with multiple functional groups and a complex stereochemical structure. Selective structural modification of brucine is challenging, and a variety of methods to achieve selective modifications at its specific site are available. The aryl moiety undergoes demethoxypentafluorophenylation, and the amide moiety undergoes the condensation with primary amine, deoxycyanation, deoxygenative reduction, and α-oximation. The tertiary amine moiety undergoes N-oxidation, formal carbene insertions of C-N or α-C-H bonds, three-component reactions with benzynes and phenols, N-amidation with nitrene, and N-alkylation with halogenated hydrocarbons. The C=C subunit undergoes dihydroxylation and hydrogenation, while the ether subunit undergoes hydrogenative cleavage. The modified structures have high potential medicinal values. As a chiral resolution reagent, brucine has been widely used in the resolution of racemic carboxylic acids, phosphoric or phosphonic acids, phenols, alcohols and some drugs. Additionally, brucine and its modified structures also find applications as chiral auxiliaries, chiral catalysts or chiral ligands in asymmetric synthesis and catalysis.
The recent advances on the structural modifications and chiral applications of Brucine are reviewed. Brucine is a naturally occuring molecule with multiple functional groups and a complex stereochemical structure. Selective structural modification of brucine is challenging, and a variety of methods to achieve selective modifications at its specific site are available. The aryl moiety undergoes demethoxypentafluorophenylation, and the amide moiety undergoes the condensation with primary amine, deoxycyanation, deoxygenative reduction, and α-oximation. The tertiary amine moiety undergoes N-oxidation, formal carbene insertions of C-N or α-C-H bonds, three-component reactions with benzynes and phenols, N-amidation with nitrene, and N-alkylation with halogenated hydrocarbons. The C=C subunit undergoes dihydroxylation and hydrogenation, while the ether subunit undergoes hydrogenative cleavage. The modified structures have high potential medicinal values. As a chiral resolution reagent, brucine has been widely used in the resolution of racemic carboxylic acids, phosphoric or phosphonic acids, phenols, alcohols and some drugs. Additionally, brucine and its modified structures also find applications as chiral auxiliaries, chiral catalysts or chiral ligands in asymmetric synthesis and catalysis.
2020, 40(12): 4122-4146
doi: 10.6023/cjoc202005003
Abstract:
1, 3-Indanedione is one of typical cyclic 1, 3-dicarbonyl compounds with one methylene unit, two carbonyl groups and fused phenyl ring. Thus, it has three contiguous reactive electrophilic and nucleophilic sites. On the other hand, 1, 3-indanedione undergoes homopolymerization to form several cyclic compounds with polycarbonyl groups under acidic or basic medium. 2-Arylidene-1, 3-indanediones derived from condensation of aromatic aldehydes with 1, 3-indanedione are also reactive α, β-unsaturated carbonyl compounds. Therefore, 1, 3-indanedione has diverse reactivities and is the key substrate in domino and multicomponent reactions. It has been widely employed to construct various spiro, bridged and fused cyclic compounds. The recent achievements on multicomponent reactions involving 1, 3-indanedione from the structures of the target compounds and the important applications on the syntheses of biologically important indanone-containing carbocyclic and heterocyclic compounds are summarized. The effects of catalyst, reaction mechanism, experimental results, reaction characteristics and limitations are briefly discussed. At last, the future development on the diverse reactions of 1, 3-indanedione is also prospected.
1, 3-Indanedione is one of typical cyclic 1, 3-dicarbonyl compounds with one methylene unit, two carbonyl groups and fused phenyl ring. Thus, it has three contiguous reactive electrophilic and nucleophilic sites. On the other hand, 1, 3-indanedione undergoes homopolymerization to form several cyclic compounds with polycarbonyl groups under acidic or basic medium. 2-Arylidene-1, 3-indanediones derived from condensation of aromatic aldehydes with 1, 3-indanedione are also reactive α, β-unsaturated carbonyl compounds. Therefore, 1, 3-indanedione has diverse reactivities and is the key substrate in domino and multicomponent reactions. It has been widely employed to construct various spiro, bridged and fused cyclic compounds. The recent achievements on multicomponent reactions involving 1, 3-indanedione from the structures of the target compounds and the important applications on the syntheses of biologically important indanone-containing carbocyclic and heterocyclic compounds are summarized. The effects of catalyst, reaction mechanism, experimental results, reaction characteristics and limitations are briefly discussed. At last, the future development on the diverse reactions of 1, 3-indanedione is also prospected.
2020, 40(12): 4147-4154
doi: 10.6023/cjoc202005024
Abstract:
As a member of chalcogen elements, tellurium is not as well known as oxygen, sulfur and selenium. As the "invisible" element in the periodic table of elements, it appears less frequently in the sight of chemists. However, in the past few decades, as the "emerald in the dark", tellurium has always played a unique role in the fields of materials science, medicine and biology, and attracted more and more chemists. In the eyes of some chemists, the performances of tellurium compounds in organic chemistry, as a "new substances", are undoubtedly eye-catching. Therefore, in recent years, there are increasing reports on the organic chemistry of tellurium compounds. In order to further understand these research progresses, the typical works are briefly summarized for readers' references.
As a member of chalcogen elements, tellurium is not as well known as oxygen, sulfur and selenium. As the "invisible" element in the periodic table of elements, it appears less frequently in the sight of chemists. However, in the past few decades, as the "emerald in the dark", tellurium has always played a unique role in the fields of materials science, medicine and biology, and attracted more and more chemists. In the eyes of some chemists, the performances of tellurium compounds in organic chemistry, as a "new substances", are undoubtedly eye-catching. Therefore, in recent years, there are increasing reports on the organic chemistry of tellurium compounds. In order to further understand these research progresses, the typical works are briefly summarized for readers' references.
2020, 40(12): 4155-4167
doi: 10.6023/cjoc202005041
Abstract:
Cancer has become one of the major threats to human health in modern society. Phototherapy including photodynamic therapy (PDT) and photothermal therapy (PTT), as a new type of tumor treatment, has received more and more attentions due to its high spatiotemporal precision, noninvasive nature, controllability, low toxicity and repeatable treatment without initial resistance. It is important to obtain a highly efficient and ideal photosensitizer for reactive oxygen species (ROS) generation for PDT. Photothermal agents with high photothermal conversion efficiency are also in urgent need for PTT. Diketopyrrolopyrrole (DPP) is an excellent type of photosensitizer and photothermal reagent because of its good structural planarity, strong electron affinity, simple synthesis, easy structure modification and high molar absorption coefficient. The research progress of DPP-based photosensitizers and photothermal agents in recent year, including structural modification of DPP, the structure-activity relationship, the mechanism of phototherapy and some representative examples is summarized. Finally, a perspective on the future development of phototherapy based on DPP is presented.
Cancer has become one of the major threats to human health in modern society. Phototherapy including photodynamic therapy (PDT) and photothermal therapy (PTT), as a new type of tumor treatment, has received more and more attentions due to its high spatiotemporal precision, noninvasive nature, controllability, low toxicity and repeatable treatment without initial resistance. It is important to obtain a highly efficient and ideal photosensitizer for reactive oxygen species (ROS) generation for PDT. Photothermal agents with high photothermal conversion efficiency are also in urgent need for PTT. Diketopyrrolopyrrole (DPP) is an excellent type of photosensitizer and photothermal reagent because of its good structural planarity, strong electron affinity, simple synthesis, easy structure modification and high molar absorption coefficient. The research progress of DPP-based photosensitizers and photothermal agents in recent year, including structural modification of DPP, the structure-activity relationship, the mechanism of phototherapy and some representative examples is summarized. Finally, a perspective on the future development of phototherapy based on DPP is presented.
2020, 40(12): 4168-4183
doi: 10.6023/cjoc202005074
Abstract:
Pyrido[1, 2-a]benzimidazole is one of the important azaheterocycles with three fused aromatic rings. These molecules containing this skeleton have wide application prospects in the fields of medicinal chemistry and materials, and their syntheses have attracted much attention in organic chemistry. According to the retrosynthetic analysis on the construction of different rings in target molecules, the research progress on the synthesis of pyrido[1, 2-a]benzimidazoles from different types of starting materials is reviewed, and its future development direction is prospected.
Pyrido[1, 2-a]benzimidazole is one of the important azaheterocycles with three fused aromatic rings. These molecules containing this skeleton have wide application prospects in the fields of medicinal chemistry and materials, and their syntheses have attracted much attention in organic chemistry. According to the retrosynthetic analysis on the construction of different rings in target molecules, the research progress on the synthesis of pyrido[1, 2-a]benzimidazoles from different types of starting materials is reviewed, and its future development direction is prospected.
2020, 40(12): 4184-4202
doi: 10.6023/cjoc202004036
Abstract:
Fingerprint can directly identify the person, and it is one of the most important physical evidence in the criminal scene. Fingerprint has always been considered as the "head of physical evidence" and plays an important role in the investigation and court proceedings. However, the fingerprint on the relevant object can not be directly observed by human eyes in actual cases, so it is also called "latent fingerprint". Although the latent fingerprint development technology has made great progress, it still faces many difficulties in the aspects of nondestructive, sensitive and efficient. And, it will bring serious difficulties to the subsequent fingerprint identification work for the criminal technicians. Therefore, it is of great significance to develop highly selective, sensitive and convenient latent fingerprint developing materials or techniques. In view of this, on the basis of the research achievements at home and abroad, the application of traditional organic materials widely used in latent fingerprint development and the new fluorescent organic materials is briefly reviewed, such as aggregation induced emission materials, conjugated polymer materials and other organic fluorescent materials, in latent fingerprint development in recent ten years. The design concept of related organic materials and the mechanism of developing latent fingerprints are summarized. Finally, the existing problems are discussed, and the future development trend of organic materials in developing latent fingerprints is prospected.
Fingerprint can directly identify the person, and it is one of the most important physical evidence in the criminal scene. Fingerprint has always been considered as the "head of physical evidence" and plays an important role in the investigation and court proceedings. However, the fingerprint on the relevant object can not be directly observed by human eyes in actual cases, so it is also called "latent fingerprint". Although the latent fingerprint development technology has made great progress, it still faces many difficulties in the aspects of nondestructive, sensitive and efficient. And, it will bring serious difficulties to the subsequent fingerprint identification work for the criminal technicians. Therefore, it is of great significance to develop highly selective, sensitive and convenient latent fingerprint developing materials or techniques. In view of this, on the basis of the research achievements at home and abroad, the application of traditional organic materials widely used in latent fingerprint development and the new fluorescent organic materials is briefly reviewed, such as aggregation induced emission materials, conjugated polymer materials and other organic fluorescent materials, in latent fingerprint development in recent ten years. The design concept of related organic materials and the mechanism of developing latent fingerprints are summarized. Finally, the existing problems are discussed, and the future development trend of organic materials in developing latent fingerprints is prospected.
2020, 40(12): 4203-4215
doi: 10.6023/cjoc202005034
Abstract:
Two alkaloids of pseudopteroxazole and ileabethoxazole, isolated from sea whip Pseudopterogorgia elisabethae, have significant antimicrobial activity against pathogen of tuberculosis:Mycobacterium tuberculosis. These two alkaloids possess similar tetracyclic skeleton, which containing four stereocenters, a fully substituted aromatic ring and an uncommon benzoxazole unit in natural products. Significant antimicrobial activity and special molecular structures attracted extensive attentions to synthetic study on pseudopteroxazole and ileabethoxazole. The progress in the total synthesis of these two alkaloids is reviewed.
Two alkaloids of pseudopteroxazole and ileabethoxazole, isolated from sea whip Pseudopterogorgia elisabethae, have significant antimicrobial activity against pathogen of tuberculosis:Mycobacterium tuberculosis. These two alkaloids possess similar tetracyclic skeleton, which containing four stereocenters, a fully substituted aromatic ring and an uncommon benzoxazole unit in natural products. Significant antimicrobial activity and special molecular structures attracted extensive attentions to synthetic study on pseudopteroxazole and ileabethoxazole. The progress in the total synthesis of these two alkaloids is reviewed.
2020, 40(12): 4216-4227
doi: 10.6023/cjoc202004053
Abstract:
Photoredox catalysis has become a universal tool to catalyze a wide variety of chemical reactions with high selectivity under mild conditions. However, traditional photocatalysis relies heavily on photocatalysts with the problems such as high price and environmental pollution. Because iodine and iodide have the advantages of cheap, non-toxic and unique photoreactivity, their application in photochemical synthesis has attracted more and more attention in recent years. The research progress of photo-redox catalysis reactions mediated by iodine and iodide in recent years is summarized, and their future outlook is also discussed.
Photoredox catalysis has become a universal tool to catalyze a wide variety of chemical reactions with high selectivity under mild conditions. However, traditional photocatalysis relies heavily on photocatalysts with the problems such as high price and environmental pollution. Because iodine and iodide have the advantages of cheap, non-toxic and unique photoreactivity, their application in photochemical synthesis has attracted more and more attention in recent years. The research progress of photo-redox catalysis reactions mediated by iodine and iodide in recent years is summarized, and their future outlook is also discussed.
2020, 40(12): 4228-4236
doi: 10.6023/cjoc202006074
Abstract:
A platinum-catalyzed syn-stereocontrolled ring-opening reaction of oxabicyclic alkenes with arylsulfonyl hydrazides was developed. This protocol exhibited high efficiency and good functional group tolerance, affording cis-2-aryl-1, 2-dihydronaphthalen-1-ols (3) or 2-aryl-naphthalenes (4) as dehydrated products in good to excellent yields under mild conditions (up to 89%). In addition, the cis-1, 2-configuration of product (1S*, 2R*)-6, 7-dibromo-2-(p-tolyl)-1, 2-dihydronaphthalen-1-ol (3db) was confirmed by X-ray single crystal diffraction analysis. Based on the results, a plausible mechanism for the ring-opening reaction was proposed. Remarkably, arylsulfonyl hydrazides were used as carboanion nucleophiles in the ring-opening reaction via releasing N2 and SO2 in situ.
A platinum-catalyzed syn-stereocontrolled ring-opening reaction of oxabicyclic alkenes with arylsulfonyl hydrazides was developed. This protocol exhibited high efficiency and good functional group tolerance, affording cis-2-aryl-1, 2-dihydronaphthalen-1-ols (3) or 2-aryl-naphthalenes (4) as dehydrated products in good to excellent yields under mild conditions (up to 89%). In addition, the cis-1, 2-configuration of product (1S*, 2R*)-6, 7-dibromo-2-(p-tolyl)-1, 2-dihydronaphthalen-1-ol (3db) was confirmed by X-ray single crystal diffraction analysis. Based on the results, a plausible mechanism for the ring-opening reaction was proposed. Remarkably, arylsulfonyl hydrazides were used as carboanion nucleophiles in the ring-opening reaction via releasing N2 and SO2 in situ.
2020, 40(12): 4237-4248
doi: 10.6023/cjoc202005057
Abstract:
Thirty-six unreported pyrimidine analogues were designed, synthesized and characterized by IR, 1H NMR, 13C NMR and HRMS. Their antifungal activities were determined against five plant pathogenic fungi namely Rhizoctonia solani, Fusarum graminearum, Helminthosporium maydis, Sclerotinia sclerotiorum and Botrytis cinerea. The results indicated that most of them revealed significant antifungal activities at 20 mg/L. Among them, 4-(furan-2-yl)-2-methyl-6-(p-tolyl)pyrimidine (2c) and 4-(4-chlorophenyl)-6-(5-methylfuran-2-yl)-2-(1H-pyrazol-1-yl)pyrimidine (3d) showed the strongest activities against Sclerotinia sclerotiorum and their median effect concentrations (EC50) were 0.072 and 0.077 mg/L, respectively, which implied that they had better antifungal activities than the commercial fungicide fluopyram (EC50=0.244 mg/L). Meanwhile, the inhibitory activities of compounds 2c and 3d were determined against succinate dehydrogenase (SDH). The results exhibited that their half inhibitory concentrations (IC50) were 0.115 and 0.121 mg/L, respectively, indicating that they also had better inhibitory activities than fluopyram (IC50=0.356 mg/L). Molecular docking studies demonstrated that the binding energy of compounds 2c, 3d and fluopyram to SDH was -32.2 kJ/mol, -31.8 kJ/mol and -28.9 kJ/mol, respectively, which represented that they had stronger affinities than fluopyram. The inhibitory activities of compounds 2c and 3d against SDH have been reported for the first time.
Thirty-six unreported pyrimidine analogues were designed, synthesized and characterized by IR, 1H NMR, 13C NMR and HRMS. Their antifungal activities were determined against five plant pathogenic fungi namely Rhizoctonia solani, Fusarum graminearum, Helminthosporium maydis, Sclerotinia sclerotiorum and Botrytis cinerea. The results indicated that most of them revealed significant antifungal activities at 20 mg/L. Among them, 4-(furan-2-yl)-2-methyl-6-(p-tolyl)pyrimidine (2c) and 4-(4-chlorophenyl)-6-(5-methylfuran-2-yl)-2-(1H-pyrazol-1-yl)pyrimidine (3d) showed the strongest activities against Sclerotinia sclerotiorum and their median effect concentrations (EC50) were 0.072 and 0.077 mg/L, respectively, which implied that they had better antifungal activities than the commercial fungicide fluopyram (EC50=0.244 mg/L). Meanwhile, the inhibitory activities of compounds 2c and 3d were determined against succinate dehydrogenase (SDH). The results exhibited that their half inhibitory concentrations (IC50) were 0.115 and 0.121 mg/L, respectively, indicating that they also had better inhibitory activities than fluopyram (IC50=0.356 mg/L). Molecular docking studies demonstrated that the binding energy of compounds 2c, 3d and fluopyram to SDH was -32.2 kJ/mol, -31.8 kJ/mol and -28.9 kJ/mol, respectively, which represented that they had stronger affinities than fluopyram. The inhibitory activities of compounds 2c and 3d against SDH have been reported for the first time.
2020, 40(12): 4267-4273
doi: 10.6023/cjoc202006025
Abstract:
An eco-friendly visible light-induced approach for the synthesis of vinyl sulfones from the reaction of nitroolefins with sulfinic acid under photocatalyst free conditions was developed. Simple operation, mild reaction conditions, broad substrate scope and good yields of the desired products made this transformation have an excellent prospect. The anti-microbial activity test showed that some of the desired products had moderate inhibitory rate against V. mali and C. glecosporioides.
An eco-friendly visible light-induced approach for the synthesis of vinyl sulfones from the reaction of nitroolefins with sulfinic acid under photocatalyst free conditions was developed. Simple operation, mild reaction conditions, broad substrate scope and good yields of the desired products made this transformation have an excellent prospect. The anti-microbial activity test showed that some of the desired products had moderate inhibitory rate against V. mali and C. glecosporioides.
2020, 40(12): 4274-4283
doi: 10.6023/cjoc202005093
Abstract:
A novel Brook rearrangement/alkylation reaction sequence of tertiary α-silyl alcohols has been developed using n-Bu4NBr as the phase transfer catalyst (PTC). A number of tertiary α-silyl alcohols are applicable to the reaction, affording the products with a quaternary carbon center in high yields (up to 71%). Moreover, the carbanions generated after the Brook rearrangement could be stabilized by the electron-withdrawing group, depressing the Brook rearrangement/protonation reaction.
A novel Brook rearrangement/alkylation reaction sequence of tertiary α-silyl alcohols has been developed using n-Bu4NBr as the phase transfer catalyst (PTC). A number of tertiary α-silyl alcohols are applicable to the reaction, affording the products with a quaternary carbon center in high yields (up to 71%). Moreover, the carbanions generated after the Brook rearrangement could be stabilized by the electron-withdrawing group, depressing the Brook rearrangement/protonation reaction.
2020, 40(12): 4284-4289
doi: 10.6023/cjoc202006030
Abstract:
In this paper, a novel transition-metal-free decarboxylative amidation of aryl α-keto acids with diphenylphosphoryl azide (DPPA) under mild conditions has been developed. The reaction proceeded smoothly to afford the corresponding primary aryl amide products in good to excellent yields under air and showed excellent functional group tolerance. Gram-scale reaction was also performed to produce the desired product in high yield. In addition, the mechanism of the present reaction was investigated.
In this paper, a novel transition-metal-free decarboxylative amidation of aryl α-keto acids with diphenylphosphoryl azide (DPPA) under mild conditions has been developed. The reaction proceeded smoothly to afford the corresponding primary aryl amide products in good to excellent yields under air and showed excellent functional group tolerance. Gram-scale reaction was also performed to produce the desired product in high yield. In addition, the mechanism of the present reaction was investigated.
2020, 40(12): 4298-4304
doi: 10.6023/cjoc202005087
Abstract:
With inexpensive potassium halide (KX) as halogen source, and oxone as oxidant, a series of allylamides underwent halocyclization reaction and generated 5-halomethyl-2-oxazolines in good to excellent isolated yields under mild conditions. The protocol showed attractive advanced features including low cost of halogen source, absence of organic byproduct, and resultant environmental-friendly nature. In addition, various useful derivatives could be expected by proper nucleophilic substitution reactions.
With inexpensive potassium halide (KX) as halogen source, and oxone as oxidant, a series of allylamides underwent halocyclization reaction and generated 5-halomethyl-2-oxazolines in good to excellent isolated yields under mild conditions. The protocol showed attractive advanced features including low cost of halogen source, absence of organic byproduct, and resultant environmental-friendly nature. In addition, various useful derivatives could be expected by proper nucleophilic substitution reactions.
2020, 40(12): 4305-4314
doi: 10.6023/cjoc202005080
Abstract:
A successful protocol has been developed for palladium-catalyzed late-stage arylation of fully substituted pyrazoles. Through screening of optimazation of reaction parameters, the most efficient reaction conditions for mono-ortho-position arylation were obtained. This reaction features a broad substrate scope, good functional group tolerance as well as good to excellent yield. Moreover, the intermolecular competition experiments and gram scale reaction were also performed. The kinetic isotopic effect (KIE) result reveled C-H bond cleavage was involved in the rate-limiting step and a plausible mechanism was proposed based on the dual-core dimeric palladacycle.
A successful protocol has been developed for palladium-catalyzed late-stage arylation of fully substituted pyrazoles. Through screening of optimazation of reaction parameters, the most efficient reaction conditions for mono-ortho-position arylation were obtained. This reaction features a broad substrate scope, good functional group tolerance as well as good to excellent yield. Moreover, the intermolecular competition experiments and gram scale reaction were also performed. The kinetic isotopic effect (KIE) result reveled C-H bond cleavage was involved in the rate-limiting step and a plausible mechanism was proposed based on the dual-core dimeric palladacycle.
2020, 40(12): 4249-4257
doi: 10.6023/cjoc202008014
Abstract:
A series of new N-pyridylpyrazole amides bearing substituted isoxazole moiety were designed and prepared based on chlorantraniliprole. These compounds were structurally determined through 1H NMR, 13C NMR and elemental analyses. Bioassay results displayed that all designed compounds showed a mortality rate of 100% towards Oriental armyworm at the dosage of 500 μg/mL. At the dosage of 100 μg/mL, the mortality rates of four compounds towards Oriental armyworm were 80%~100%. Two compounds had 40%~50% insecticidal activities towards Oriental armyworm at the concentration of 20 μg/mL. At the concentration of 500 μg/mL, five compounds demonstrated 90%~100% insecticidal activities against Aphis medicaginis. Moreover, at the dosage of 500 μg/mL, two compounds exhibited 70%~80% insecticidal activities against Tetranychus cinnabarinus.
A series of new N-pyridylpyrazole amides bearing substituted isoxazole moiety were designed and prepared based on chlorantraniliprole. These compounds were structurally determined through 1H NMR, 13C NMR and elemental analyses. Bioassay results displayed that all designed compounds showed a mortality rate of 100% towards Oriental armyworm at the dosage of 500 μg/mL. At the dosage of 100 μg/mL, the mortality rates of four compounds towards Oriental armyworm were 80%~100%. Two compounds had 40%~50% insecticidal activities towards Oriental armyworm at the concentration of 20 μg/mL. At the concentration of 500 μg/mL, five compounds demonstrated 90%~100% insecticidal activities against Aphis medicaginis. Moreover, at the dosage of 500 μg/mL, two compounds exhibited 70%~80% insecticidal activities against Tetranychus cinnabarinus.
2020, 40(12): 4258-4266
doi: 10.6023/cjoc202005077
Abstract:
Phenanthrene derivatives play an important role in pharmaceutical chemistry and material science. Due to its advantages of green, mild reaction conditions and great application potential, visible light catalysis has become a powerful tool in organic synthesis. In this paper, under the catalysis of photocatalyst Ir[dF(CF3)ppy]2(dtbbpy)PF6, a series of 10-phenanthrenol derivatives were synthesized from 2-arylbenzoyl acetate derivatives in moderate to good yields through intramolecular cycloaromatization. In addition, the plausible reaction mechanism was also proposed.
Phenanthrene derivatives play an important role in pharmaceutical chemistry and material science. Due to its advantages of green, mild reaction conditions and great application potential, visible light catalysis has become a powerful tool in organic synthesis. In this paper, under the catalysis of photocatalyst Ir[dF(CF3)ppy]2(dtbbpy)PF6, a series of 10-phenanthrenol derivatives were synthesized from 2-arylbenzoyl acetate derivatives in moderate to good yields through intramolecular cycloaromatization. In addition, the plausible reaction mechanism was also proposed.
2020, 40(12): 4290-4297
doi: 10.6023/cjoc202005049
Abstract:
Three difluoroboron (BF2) β-diketonates 2a~2c including different aromatic ring systems were synthesized from nopinone which was the derivative of renewable natural β-pinene. In the solid state, compounds 2a~2c exhibit different fluorescent colors. Compounds 2b and 2c showed the positive solvatochromism phenomenon, and they have different fluorescence colors in different polar solvents. In addition, compounds 2b and 2c have significant aggregation-induced emission (AIE) effect. Compounds 2b and 2c were made into electroluminescent devices Ⅰ and Ⅱ, and device Ⅰ and Ⅱ emit green light and yellow light, respectively. The results indicate that compounds 2b and 2c have good application prospects as organic solid luminescent materials.
Three difluoroboron (BF2) β-diketonates 2a~2c including different aromatic ring systems were synthesized from nopinone which was the derivative of renewable natural β-pinene. In the solid state, compounds 2a~2c exhibit different fluorescent colors. Compounds 2b and 2c showed the positive solvatochromism phenomenon, and they have different fluorescence colors in different polar solvents. In addition, compounds 2b and 2c have significant aggregation-induced emission (AIE) effect. Compounds 2b and 2c were made into electroluminescent devices Ⅰ and Ⅱ, and device Ⅰ and Ⅱ emit green light and yellow light, respectively. The results indicate that compounds 2b and 2c have good application prospects as organic solid luminescent materials.
2020, 40(12): 4315-4321
doi: 10.6023/cjoc202008031
Abstract:
In search of new N-heterocyclic compounds possessing good biological activities, 17 novel pyrazole oxime derivatives were designed and synthesized by introducing benzotriazole moiety into pyrazole oxime skeleton based on fenpyroximate. Their structures were tested by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data displayed that 3 compounds showed 70%~100% insecticidal activities towards Tetranychus cinnabarinus at 20 μg/mL. 6 compounds possessed 90%~100% mortality rates towards Aphis medicaginis at 20 μg/mL. Moreover, 16 compounds displayed more than 80% insecticidal activities against Mythimna separata (Walker) at 500 μg/mL.
In search of new N-heterocyclic compounds possessing good biological activities, 17 novel pyrazole oxime derivatives were designed and synthesized by introducing benzotriazole moiety into pyrazole oxime skeleton based on fenpyroximate. Their structures were tested by 1H NMR, 13C NMR and elemental analysis. Preliminary bioassay data displayed that 3 compounds showed 70%~100% insecticidal activities towards Tetranychus cinnabarinus at 20 μg/mL. 6 compounds possessed 90%~100% mortality rates towards Aphis medicaginis at 20 μg/mL. Moreover, 16 compounds displayed more than 80% insecticidal activities against Mythimna separata (Walker) at 500 μg/mL.
2020, 40(12): 4322-4327
doi: 10.6023/cjoc202005059
Abstract:
A novel cyclization reaction by using hexachloroacetone as C2 synthon has been studied. The optimal condition was obtained by synthesis of bibenzothiazole in the presence hexachloroacetone in water. Experimental results showed that the nucleophilicity of substrates played a key role in the cyclization reaction, and catalytical amount of oxygen in reactions was also vital to trigger ring fusion in the formation of target compounds. Accordingly, the mechanism of cyclization reaction was proposed:the thiazole ring is formed in the first place by a nucleophillic attack of 2-aminobenzenethiol, followed by CCl3 cleavage from hexachloroacetone. Then the second 2-aminobenzenethiol launches another nucleophilic attack, and three chloride ions leave to form the second thiazole ring. The method was applied to the substrates of 2, 5-diaminobenzene-1, 4-dithiol and benzene-1, 2, 4, 5-tetraamine, respectively and two polymers of polyphenylene dithiazole and polyphenylene diimidazole were successfully prepared. The experimental conditions were mild, the yield was high and the application value was high.
A novel cyclization reaction by using hexachloroacetone as C2 synthon has been studied. The optimal condition was obtained by synthesis of bibenzothiazole in the presence hexachloroacetone in water. Experimental results showed that the nucleophilicity of substrates played a key role in the cyclization reaction, and catalytical amount of oxygen in reactions was also vital to trigger ring fusion in the formation of target compounds. Accordingly, the mechanism of cyclization reaction was proposed:the thiazole ring is formed in the first place by a nucleophillic attack of 2-aminobenzenethiol, followed by CCl3 cleavage from hexachloroacetone. Then the second 2-aminobenzenethiol launches another nucleophilic attack, and three chloride ions leave to form the second thiazole ring. The method was applied to the substrates of 2, 5-diaminobenzene-1, 4-dithiol and benzene-1, 2, 4, 5-tetraamine, respectively and two polymers of polyphenylene dithiazole and polyphenylene diimidazole were successfully prepared. The experimental conditions were mild, the yield was high and the application value was high.
2020, 40(12): 4332-4338
doi: 10.6023/cjoc202006056
Abstract:
In search of novel neonicotinoid insecticides with potent bioactivities, a series of 1, 2-dithiocyclopentenone derivatives were designed and synthesized by introducing dithiocyclopentenone into neonicotinoids skeleton. The structures of all compounds were confirmed by nuclear magnetic resonance (NMR) and high resolution mass spectrometry (HRMS). Biological activities of all the title compounds were evaluated systematically. Preliminary bioassays indicated that all synthesized compounds exhibited moderate insecticidal activities. 4-Chloro-5-(((6-chloropyridin-3-yl)methyl)(methyl)amino)-3H-1, 2-di-thiol-3-one (3a), 4-chloro-5-(((6-chloropyridin-3-yl)methyl)(ethyl)amino)-3H-1, 2-dithiol-3-one (3b), 4-chloro-5-(((6-chloro-pyridin-3-yl)methyl)(propyl)amino)-3H-1, 2-dithiol-3-one (3c) and 4-chloro-5-(((6-chloropyridin-3-yl)methyl)(2, 2-difluoro-ethyl)amino)-3H-1, 2-dithiol-3-one (3g) exhibited >90% mortality rate against Aphis craccivora at 100 μg/mL. Compound 3g exhibited 40% insecticidal activity to aphids at 4 μg/mL and >70% mortality rate against Nilaparvata Lugens at 100 μg/mL, and could be utilized in insecticide research with further optimization.
In search of novel neonicotinoid insecticides with potent bioactivities, a series of 1, 2-dithiocyclopentenone derivatives were designed and synthesized by introducing dithiocyclopentenone into neonicotinoids skeleton. The structures of all compounds were confirmed by nuclear magnetic resonance (NMR) and high resolution mass spectrometry (HRMS). Biological activities of all the title compounds were evaluated systematically. Preliminary bioassays indicated that all synthesized compounds exhibited moderate insecticidal activities. 4-Chloro-5-(((6-chloropyridin-3-yl)methyl)(methyl)amino)-3H-1, 2-di-thiol-3-one (3a), 4-chloro-5-(((6-chloropyridin-3-yl)methyl)(ethyl)amino)-3H-1, 2-dithiol-3-one (3b), 4-chloro-5-(((6-chloro-pyridin-3-yl)methyl)(propyl)amino)-3H-1, 2-dithiol-3-one (3c) and 4-chloro-5-(((6-chloropyridin-3-yl)methyl)(2, 2-difluoro-ethyl)amino)-3H-1, 2-dithiol-3-one (3g) exhibited >90% mortality rate against Aphis craccivora at 100 μg/mL. Compound 3g exhibited 40% insecticidal activity to aphids at 4 μg/mL and >70% mortality rate against Nilaparvata Lugens at 100 μg/mL, and could be utilized in insecticide research with further optimization.
2020, 40(12): 4344-4349
doi: 10.6023/cjoc202006004
Abstract:
Polyurethane materials are widely used in biomedical fields such as implantable catheters and drug delivery. However, their blood compatibility is difficult to meet the rigorous requirements needed for a new generation of biomedical devices. A series of polyurethane elastomers were prepared using polycarbonate diols (PC), polyoxytertramethylene glycol (PTMG), isophorone diisocyanate (IPDI) and chain extender (BDO, E-300) as raw materials. The properties of polyurethane elastomers were investigated by FT-IR spectrum, differential scanning calorimeter (DSC) analysis, mechanical test, water contact angle measurement, hemolysis and cell compatibility test. The mechanical results show that the materials have superior tensile strength and elongation, meanwhile, the homolysis and cells compatibility tests exhibit that they have good bio-compatibility. In addition, the materials can achieve the best performance by using IPDI as well as chain extender E-300 as the hard segment and PC as the soft segment.
Polyurethane materials are widely used in biomedical fields such as implantable catheters and drug delivery. However, their blood compatibility is difficult to meet the rigorous requirements needed for a new generation of biomedical devices. A series of polyurethane elastomers were prepared using polycarbonate diols (PC), polyoxytertramethylene glycol (PTMG), isophorone diisocyanate (IPDI) and chain extender (BDO, E-300) as raw materials. The properties of polyurethane elastomers were investigated by FT-IR spectrum, differential scanning calorimeter (DSC) analysis, mechanical test, water contact angle measurement, hemolysis and cell compatibility test. The mechanical results show that the materials have superior tensile strength and elongation, meanwhile, the homolysis and cells compatibility tests exhibit that they have good bio-compatibility. In addition, the materials can achieve the best performance by using IPDI as well as chain extender E-300 as the hard segment and PC as the soft segment.
2020, 40(12): 4350-4356
doi: 10.6023/cjoc202007029
Abstract:
In search of new pyrazole amide derivatives with wonderful bioactivities, fifteen novel pyrazole amide compounds were designed and synthesized by introducing substituted oxazole unit into pyrazole amide skeleton based on the lead compound tebufenpyrad. The structures of the title compounds were confirmed by 1H NMR, 13C NMR and elemental analysis. The preliminary bioassay data exhibited that most of target compounds had more than 90% insecticidal activities against Oriental armyworm at the concentration of 500 μg/mL. At the concentration of 500 μg/mL, one compound displayed 100% mortality rate against Aphis medicaginis. In addition, two compounds showed 30% insecticidal activity against Tetranychus cinnabarinus at the concentration of 500 μg/mL.
In search of new pyrazole amide derivatives with wonderful bioactivities, fifteen novel pyrazole amide compounds were designed and synthesized by introducing substituted oxazole unit into pyrazole amide skeleton based on the lead compound tebufenpyrad. The structures of the title compounds were confirmed by 1H NMR, 13C NMR and elemental analysis. The preliminary bioassay data exhibited that most of target compounds had more than 90% insecticidal activities against Oriental armyworm at the concentration of 500 μg/mL. At the concentration of 500 μg/mL, one compound displayed 100% mortality rate against Aphis medicaginis. In addition, two compounds showed 30% insecticidal activity against Tetranychus cinnabarinus at the concentration of 500 μg/mL.
2020, 40(12): 4357-4363
doi: 10.6023/cjoc202005078
Abstract:
2, 4, 6-Triarylpyrimidines were synthesized via a simple, efficient, one-pot, three-component reaction from 1, 3-dikeones, benzaldehydes and ammonium acetate under solvent-free and catalyst-free conditions in good to excellent yields. This "green" methodology provides an eco-friendly protocol for the construction of the pyrimidine framework.
2, 4, 6-Triarylpyrimidines were synthesized via a simple, efficient, one-pot, three-component reaction from 1, 3-dikeones, benzaldehydes and ammonium acetate under solvent-free and catalyst-free conditions in good to excellent yields. This "green" methodology provides an eco-friendly protocol for the construction of the pyrimidine framework.
2020, 40(12): 4328-4331
doi: 10.6023/cjoc202006034
Abstract:
By silica gel, Sephadex LH-20 column chromatography as well as preparative high performance liquid chromatography (HPLC), four previously undescribed α-pyrones sharing same primary structure were isolated from the brown rice solid medium of Fusarium tricinctum. Their structures were elucidated by spectroscopic analyses and their absolute configurations were finally confirmed by a modified Snatzke's method.
By silica gel, Sephadex LH-20 column chromatography as well as preparative high performance liquid chromatography (HPLC), four previously undescribed α-pyrones sharing same primary structure were isolated from the brown rice solid medium of Fusarium tricinctum. Their structures were elucidated by spectroscopic analyses and their absolute configurations were finally confirmed by a modified Snatzke's method.
2020, 40(12): 4339-4343
doi: 10.6023/cjoc202007022
Abstract:
Two reaction-based water-soluble boron-dipyrromethene (BODIPY) fluorescent probes, Ac-Phe-BODIPY and Ac-BODIPY, were developed for peroxynitrite (ONOO-) measurement. High sensitivity, low detection limit and excellent selectivity toward ONOO- were obtained for determining reactive oxygen species (ROS) and reactive nitrogen species (RNS). The reaction-based probe Ac-Phe-BODIPY was hydrolyzed into BODIPY-1 which was isolated by column chromatography and proved by 1H NMR and ESI-MS. The characterization results revealed the photoinduced electron transfer (PET) mechanism which was simultaneously in agreement with density functional theory (DFT) calculation.
Two reaction-based water-soluble boron-dipyrromethene (BODIPY) fluorescent probes, Ac-Phe-BODIPY and Ac-BODIPY, were developed for peroxynitrite (ONOO-) measurement. High sensitivity, low detection limit and excellent selectivity toward ONOO- were obtained for determining reactive oxygen species (ROS) and reactive nitrogen species (RNS). The reaction-based probe Ac-Phe-BODIPY was hydrolyzed into BODIPY-1 which was isolated by column chromatography and proved by 1H NMR and ESI-MS. The characterization results revealed the photoinduced electron transfer (PET) mechanism which was simultaneously in agreement with density functional theory (DFT) calculation.
2020, 40(12): 4364-4366
doi: 10.6023/cjoc202000083
Abstract:
2020, 40(12): 4367-4369
doi: 10.6023/cjoc202000084
Abstract:
2020, 40(12): 4370-4371
doi: 10.6023/cjoc202000085
Abstract:
2020, 40(12): 4372-4374
doi: 10.6023/cjoc202000086
Abstract:
2020, 40(12): 4375-4376
doi: 10.6023/cjoc202000087
Abstract:
2020, 40(12): 4377-4379
doi: 10.6023/cjoc202000088
Abstract:
2020, 40(12): 4382-4383
doi: 10.6023/cjoc202000090
Abstract:
2020, 40(12): 4384-4386
doi: 10.6023/cjoc202000091
Abstract:
2020, 40(12): 4387-4389
doi: 10.6023/cjoc202000092
Abstract:
