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2019 Volume 39 Issue 12
2019, 39(12): 3315-3327
doi: 10.6023/cjoc201908020
Abstract:
Transition-metal-catalyzed Suzuki-Miyaura cross-coupling is one of the most powerful transformations for C-C biaryl bond formation at present. With the increasing demand for green chemistry, water as solvent for the Suzuki-Miyaura cross-coupling reactions has been of widespread interest. The literature in recent years on the Suzuki-Miyaura cross-coupling reactions by heterogeneous or homogeneous catalysis in water is reviewed, and their perspectives for further developments are also presented.
Transition-metal-catalyzed Suzuki-Miyaura cross-coupling is one of the most powerful transformations for C-C biaryl bond formation at present. With the increasing demand for green chemistry, water as solvent for the Suzuki-Miyaura cross-coupling reactions has been of widespread interest. The literature in recent years on the Suzuki-Miyaura cross-coupling reactions by heterogeneous or homogeneous catalysis in water is reviewed, and their perspectives for further developments are also presented.
2019, 39(12): 3328-3337
doi: 10.6023/cjoc201907005
Abstract:
Oxygen-bearing structures are attractive synthetic targets due to their wide presence in a great number of natural products and biologically active molecules, and their role as useful synthons in organic synthesis. Thus, the preparation of O-bearing compounds has been an important topic. Transition metal-catalyzed aerobic oxygenation strategy has emerged as a novel and efficient methodology for constructing C-C bonds and C-heteroatom bonds. This strategy has become one of the most important and useful synthetic method in organic synthesis of O-bearing compounds. Based on the previous work of our group and others, herein, the new applications of transition metal-catalyzed oxygenation of C-H bond activation and C-C bond cleavage with oxygen as oxygen source are discussed. The recent progress in trans-metal catalytic oxygen insertion of ketones, aldehydes, alkene, alkynes, arene and aromatic heterocyclic compounds has been reviewed. Transition metal-catalysts can initiate oxygen insertion reaction of free radical pathway and realize selective insertion of oxygen radicals under oxygen oxidation. These reactions are characterized by mild conditions, environmental protection and highly atom economy.
Oxygen-bearing structures are attractive synthetic targets due to their wide presence in a great number of natural products and biologically active molecules, and their role as useful synthons in organic synthesis. Thus, the preparation of O-bearing compounds has been an important topic. Transition metal-catalyzed aerobic oxygenation strategy has emerged as a novel and efficient methodology for constructing C-C bonds and C-heteroatom bonds. This strategy has become one of the most important and useful synthetic method in organic synthesis of O-bearing compounds. Based on the previous work of our group and others, herein, the new applications of transition metal-catalyzed oxygenation of C-H bond activation and C-C bond cleavage with oxygen as oxygen source are discussed. The recent progress in trans-metal catalytic oxygen insertion of ketones, aldehydes, alkene, alkynes, arene and aromatic heterocyclic compounds has been reviewed. Transition metal-catalysts can initiate oxygen insertion reaction of free radical pathway and realize selective insertion of oxygen radicals under oxygen oxidation. These reactions are characterized by mild conditions, environmental protection and highly atom economy.
2019, 39(12): 3353-3362
doi: 10.6023/cjoc201907014
Abstract:
Water is a medium for reaction in living organisms, which is safe, cheap and easy to obtain, and visible light is a clean and renewable natural resource. Exploring the controllable free radical reaction under the illumination condition in water and developing a simple, green and efficient synthesis method not only conform to the current green chemistry theme, but also have an important scientific significance in theory and practical application. The classification and review of visible light catalysis in aqueous phase have been carried out in recent years, and the corresponding mechanisms are discussed.
Water is a medium for reaction in living organisms, which is safe, cheap and easy to obtain, and visible light is a clean and renewable natural resource. Exploring the controllable free radical reaction under the illumination condition in water and developing a simple, green and efficient synthesis method not only conform to the current green chemistry theme, but also have an important scientific significance in theory and practical application. The classification and review of visible light catalysis in aqueous phase have been carried out in recent years, and the corresponding mechanisms are discussed.
2019, 39(12): 3363-3374
doi: 10.6023/cjoc201906026
Abstract:
Amino compounds have a wide range of applications in the fields of organic chemistry, medicinal chemistry and functional materials. The efficient construction of C-N bonds has important research significance. Conventional amination reactions to construct C-N bonds require pre-functionalization of the substrate and inevitably produce quantitative halogenate by-products. The C-H amination reaction is directly based on hydrocarbons. The reaction has the advantages of "step" and "atomic" economy, in line with the green chemistry concept. Transition metal cobalt has the advantage of low toxicity and low cost. As a catalyst for C-H amination reaction, it exhibits its unique catalytic properties and attracts the attention of chemists. The research progress of cobalt-catalyzed C-H amination in recent years is summarized. At the same time, the challenges and development prospects of the research field are summarized and forecasted.
Amino compounds have a wide range of applications in the fields of organic chemistry, medicinal chemistry and functional materials. The efficient construction of C-N bonds has important research significance. Conventional amination reactions to construct C-N bonds require pre-functionalization of the substrate and inevitably produce quantitative halogenate by-products. The C-H amination reaction is directly based on hydrocarbons. The reaction has the advantages of "step" and "atomic" economy, in line with the green chemistry concept. Transition metal cobalt has the advantage of low toxicity and low cost. As a catalyst for C-H amination reaction, it exhibits its unique catalytic properties and attracts the attention of chemists. The research progress of cobalt-catalyzed C-H amination in recent years is summarized. At the same time, the challenges and development prospects of the research field are summarized and forecasted.
2019, 39(12): 3375-3383
doi: 10.6023/cjoc201906029
Abstract:
As an important endogenous gas transmitter, carbon monoxide (CO) has been found taking part in multiple physiological and pathological processes for life. Therefore, the selective recognition and sensitive detection of CO are of great biological and medical significance. Fluorescent probe method is highlighted by its good selectivity, high sensitivity, suitable for high-throughput screening, especially noninvasive detection, and real-time monitoring in situ. Therefore, the development of fluorescent probes for intracellular CO has been becoming one of the hot topics. Herein, the progress during the last decade of fluorescent molecular probes based on the small molecules for CO detection is reviewed. These fluorescent probes are classified and concluded according to the design concepts, detection mechanism, and biological applications. In addition, the relationship between molecular structures and properties is elucidated. Finally, the challenge and application prospects for the development of CO fluorescent probes are also discussed.
As an important endogenous gas transmitter, carbon monoxide (CO) has been found taking part in multiple physiological and pathological processes for life. Therefore, the selective recognition and sensitive detection of CO are of great biological and medical significance. Fluorescent probe method is highlighted by its good selectivity, high sensitivity, suitable for high-throughput screening, especially noninvasive detection, and real-time monitoring in situ. Therefore, the development of fluorescent probes for intracellular CO has been becoming one of the hot topics. Herein, the progress during the last decade of fluorescent molecular probes based on the small molecules for CO detection is reviewed. These fluorescent probes are classified and concluded according to the design concepts, detection mechanism, and biological applications. In addition, the relationship between molecular structures and properties is elucidated. Finally, the challenge and application prospects for the development of CO fluorescent probes are also discussed.
2019, 39(12): 3384-3398
doi: 10.6023/cjoc201904013
Abstract:
N-Confused porphyrin, as the typical representative of porphyrinoids, is an isomer of porphyrin. It is an important member of porphyrins, which has attracted extensive attention of chemists recently because of its unique chemical structure and reactivity. Significance, structures and properties of N-confused porphyrins are briefly introduced. Progress in the synthesis of N-confused porphyrins and their applications in the area of catalytic chemistry, biological chemistry and materials chemistry are reviewed emphatically. The development status of expanded N-confused porphyrins and other confused porphyrinoids are also briefly introduced. Further development of N-confused porphyrin chemisty is proposed in the end.
N-Confused porphyrin, as the typical representative of porphyrinoids, is an isomer of porphyrin. It is an important member of porphyrins, which has attracted extensive attention of chemists recently because of its unique chemical structure and reactivity. Significance, structures and properties of N-confused porphyrins are briefly introduced. Progress in the synthesis of N-confused porphyrins and their applications in the area of catalytic chemistry, biological chemistry and materials chemistry are reviewed emphatically. The development status of expanded N-confused porphyrins and other confused porphyrinoids are also briefly introduced. Further development of N-confused porphyrin chemisty is proposed in the end.
2019, 39(12): 3399-3413
doi: 10.6023/cjoc201904016
Abstract:
Color-tunable and white light-emitting lanthanide-based complex/coordination polymer materials have attracted increasing interest recently due to the exceptional luminescent and chromogenic properties. Recent advances from 2014 to 2018 on white-light-emitting lanthanide-based materials are classifiedly highlighted in light of different aggregate states and lanthanide species in the coordination assemblies. The future advances in this field are also predicted.
Color-tunable and white light-emitting lanthanide-based complex/coordination polymer materials have attracted increasing interest recently due to the exceptional luminescent and chromogenic properties. Recent advances from 2014 to 2018 on white-light-emitting lanthanide-based materials are classifiedly highlighted in light of different aggregate states and lanthanide species in the coordination assemblies. The future advances in this field are also predicted.
2019, 39(12): 3414-3437
doi: 10.6023/cjoc201906015
Abstract:
In recent years, molecular fluorescent probes have attracted extensive attention due to their high sensitivity, high selectivity, specificity and simplicity of design. Perylene tetracarboxylic diimide derivatives (PDIs) are well known for their excellent photothermal stability, chemical stability, high fluorescence quantum yield, large stokes shift and easy modification. Therefore, they can be used as excellent fluorophores. PDI itself has strong electron-withdrawing group and easily to be reduced but it is hard to be oxidized. However, due to their inherent structure, the poor water solubility and aggregatable ablility limited their applications in biological fields. The water solubility of PDI was improved by introducing hydrophilic groups into the structure. Therefore, the PDIs with the unique advantages will have potential application values in the field of fluorescence probe and has been developed rapidly for the past few years. The development of PDI as a chromophore in fluorescent probe for the detection of ion, gas, biomolecules, etc. is systematically summarized. Meanwhile, the design of the probes, fluorescence response mechanism and application of the probe are also discussed. Finally, a novel type of PDI fluorescent probe is proposed. The challenge of construction of the PDIs and future development are also reviewed.
In recent years, molecular fluorescent probes have attracted extensive attention due to their high sensitivity, high selectivity, specificity and simplicity of design. Perylene tetracarboxylic diimide derivatives (PDIs) are well known for their excellent photothermal stability, chemical stability, high fluorescence quantum yield, large stokes shift and easy modification. Therefore, they can be used as excellent fluorophores. PDI itself has strong electron-withdrawing group and easily to be reduced but it is hard to be oxidized. However, due to their inherent structure, the poor water solubility and aggregatable ablility limited their applications in biological fields. The water solubility of PDI was improved by introducing hydrophilic groups into the structure. Therefore, the PDIs with the unique advantages will have potential application values in the field of fluorescence probe and has been developed rapidly for the past few years. The development of PDI as a chromophore in fluorescent probe for the detection of ion, gas, biomolecules, etc. is systematically summarized. Meanwhile, the design of the probes, fluorescence response mechanism and application of the probe are also discussed. Finally, a novel type of PDI fluorescent probe is proposed. The challenge of construction of the PDIs and future development are also reviewed.
2019, 39(12): 3338-3352
doi: 10.6023/cjoc201904068
Abstract:
Recently, the direct incorporation of heteroatom into imidazole-fused heterocycles through transition metal-free C-H functionalization has rapidly been advanced and become an eco-friendly synthetic tool for the synthesis of functionalized natural or bioactive molecules such as (hetero)arenes, olefins, carbonyl compounds. In particular, the C-H functionalization of imidazole-fused heterocycles has been considered to be the most important since it can lead to a new class of biologically active compounds. The recent progress in the incorporation of heteroatom into imidazole-fused heterocycles through transition metal-free C-H functionalization is introduced, and their mechanisms from a new perspective are also elaborated.
Recently, the direct incorporation of heteroatom into imidazole-fused heterocycles through transition metal-free C-H functionalization has rapidly been advanced and become an eco-friendly synthetic tool for the synthesis of functionalized natural or bioactive molecules such as (hetero)arenes, olefins, carbonyl compounds. In particular, the C-H functionalization of imidazole-fused heterocycles has been considered to be the most important since it can lead to a new class of biologically active compounds. The recent progress in the incorporation of heteroatom into imidazole-fused heterocycles through transition metal-free C-H functionalization is introduced, and their mechanisms from a new perspective are also elaborated.
2019, 39(12): 3438-3445
doi: 10.6023/cjoc201909008
Abstract:
An iron catalyzed deoxygenative diborylation of ketones to access a variety of internal gem-diboronates has been developed. A scale-up synthesis of such gem-diboronates is also applicable under this condition. Meanwhile, common organic solvent acetone was used as start material to synthesize corresponding internal gem-diboronate, and further mono- or di-functionalization of such internal gem-diboronate has also been explored to demonstrate the synthetic potential of internal gem-diboronates.
An iron catalyzed deoxygenative diborylation of ketones to access a variety of internal gem-diboronates has been developed. A scale-up synthesis of such gem-diboronates is also applicable under this condition. Meanwhile, common organic solvent acetone was used as start material to synthesize corresponding internal gem-diboronate, and further mono- or di-functionalization of such internal gem-diboronate has also been explored to demonstrate the synthetic potential of internal gem-diboronates.
2019, 39(12): 3467-3474
doi: 10.6023/cjoc201907010
Abstract:
A graphene based hybrid with copper nanoparticles (Cu-Cu2O/GO-NH2) as a heterogeneous catalyst for the preparation of β-ketophosphonates was investigated. Compared with traditional homogeneous catalysis, Cu-Cu2O/GO-NH2 catalyst can be recovered from the reaction system. The present methodology provides a facile and efficient approach to access a wide range of β-ketophosphonates in good yields. This reaction can be conducted under base-free conditions without any external co-catalysts, which provides an alternative strategy for the synthesis of β-ketophosphonates.
A graphene based hybrid with copper nanoparticles (Cu-Cu2O/GO-NH2) as a heterogeneous catalyst for the preparation of β-ketophosphonates was investigated. Compared with traditional homogeneous catalysis, Cu-Cu2O/GO-NH2 catalyst can be recovered from the reaction system. The present methodology provides a facile and efficient approach to access a wide range of β-ketophosphonates in good yields. This reaction can be conducted under base-free conditions without any external co-catalysts, which provides an alternative strategy for the synthesis of β-ketophosphonates.
2019, 39(12): 3505-3515
doi: 10.6023/cjoc201903072
Abstract:
A series of tacrine-3-n-butylphthalide hybrids have been designed, synthesized and evaluated as multifunctional cholinesterase (ChE) inhibitors against Alzheimer's disease (AD). The result showed that all the target compounds exhibited inhibitory activity on acetylcholinesterase (AChE) and butylcholinesterase (BuChE). Especially, 3-butyl-6-((7-((1, 2, 3, 4-tetra-hydroacridin-9-yl)amino)heptyl)oxy)isobenzofuran-1(3H)-one (10b) displayed the greatest ability to inhibit AChE (IC50=38.65 nmol·L-1), which was 5-fold greater than that of tacrine (IC50=200.70 nmol·L-1). 3-Butyl-6-((8-((6-chloro-1, 2, 3, 4-tetrahydroacridin-9-yl)amino)heptyl)oxy)isobenzofuran-1(3H)-one (10g) displayed the greatest ability to inhibit BuChE (IC50=33.69 nmol·L-1), which was close to tacrine (IC50=27.12 nmol·L-1) and 220-fold greater than that of donepezil (IC50=7530 nmol·L-1). In rat Aβ-induced injury model of hippocampal neurons, the effect of compounds on reactive oxygen species (ROS) levels in rat hippocampal have been evaluated, and the results indicated that most of these compounds had potent inhibitory activity for rat hippocampal neuronal cells secreting ROS induced by Aβ1-42.
A series of tacrine-3-n-butylphthalide hybrids have been designed, synthesized and evaluated as multifunctional cholinesterase (ChE) inhibitors against Alzheimer's disease (AD). The result showed that all the target compounds exhibited inhibitory activity on acetylcholinesterase (AChE) and butylcholinesterase (BuChE). Especially, 3-butyl-6-((7-((1, 2, 3, 4-tetra-hydroacridin-9-yl)amino)heptyl)oxy)isobenzofuran-1(3H)-one (10b) displayed the greatest ability to inhibit AChE (IC50=38.65 nmol·L-1), which was 5-fold greater than that of tacrine (IC50=200.70 nmol·L-1). 3-Butyl-6-((8-((6-chloro-1, 2, 3, 4-tetrahydroacridin-9-yl)amino)heptyl)oxy)isobenzofuran-1(3H)-one (10g) displayed the greatest ability to inhibit BuChE (IC50=33.69 nmol·L-1), which was close to tacrine (IC50=27.12 nmol·L-1) and 220-fold greater than that of donepezil (IC50=7530 nmol·L-1). In rat Aβ-induced injury model of hippocampal neurons, the effect of compounds on reactive oxygen species (ROS) levels in rat hippocampal have been evaluated, and the results indicated that most of these compounds had potent inhibitory activity for rat hippocampal neuronal cells secreting ROS induced by Aβ1-42.
2019, 39(12): 3524-3531
doi: 10.6023/cjoc201905006
Abstract:
A copper-catalyzed cyanoisopropylation/cyclization cascade of N-alkenylacrylamides is presented, providing a straightforward and chemoselective access to 1, 3-dihydropyrrol-2-ones. In acrylamide-based radical cyclization, radical-trapping groups are mainly restricted to aryl, alkynyl or cyano group. But in this reaction, the enaminic double bond was used as an inbuilt radical trap, while the olefinic bond of the acrylamidyl moiety acted as the radical acceptor. Such chemoselectivity might be attributed to polarity matching.
A copper-catalyzed cyanoisopropylation/cyclization cascade of N-alkenylacrylamides is presented, providing a straightforward and chemoselective access to 1, 3-dihydropyrrol-2-ones. In acrylamide-based radical cyclization, radical-trapping groups are mainly restricted to aryl, alkynyl or cyano group. But in this reaction, the enaminic double bond was used as an inbuilt radical trap, while the olefinic bond of the acrylamidyl moiety acted as the radical acceptor. Such chemoselectivity might be attributed to polarity matching.
2019, 39(12): 3446-3453
doi: 10.6023/cjoc201908022
Abstract:
An amphiphilic derivative FA-DNJ-C6 with deoxynojirimycin modification was synthesized. The self-assembly behavior of FA-DNJ-C6 was studied by a surface tension test, dynamic light scattering test (DLS) and transmission electron microscopy (TEM). FA-DNJ-C6 formed stable supramolecular self-assembly in aqueous solution. Furthermore, the glycosidase inhibition activities of FA-DNJ-C6 were studied. FA-DNJ-C6 as multivalent glycosidase inhibitor showed potent glycosidase effect against α-mannosidase with Ki value of (0.107±0.021) μmol/L, an increase of approximately 339-fold compared with the control drug of miglitol, which was due to the multivalent binding sites in α-mannosidase.
An amphiphilic derivative FA-DNJ-C6 with deoxynojirimycin modification was synthesized. The self-assembly behavior of FA-DNJ-C6 was studied by a surface tension test, dynamic light scattering test (DLS) and transmission electron microscopy (TEM). FA-DNJ-C6 formed stable supramolecular self-assembly in aqueous solution. Furthermore, the glycosidase inhibition activities of FA-DNJ-C6 were studied. FA-DNJ-C6 as multivalent glycosidase inhibitor showed potent glycosidase effect against α-mannosidase with Ki value of (0.107±0.021) μmol/L, an increase of approximately 339-fold compared with the control drug of miglitol, which was due to the multivalent binding sites in α-mannosidase.
2019, 39(12): 3454-3459
doi: 10.6023/cjoc201904081
Abstract:
Allylsilanes have emerged as synthetically useful intermediates that can undergo a variety of chemical transformations and have been found versatile applications in C-C bond construction as well as in preparation of complex molecules. Exploration on the stereoselective route to functionalized allylsilanes is of great significance for the development of organic synthetic methodology. An efficient pathway to a series of novel alkoxy-substituted homoiodio-allylsilanes via the Julia olefination of silylmethyl cyclopropyl carbinols was described. Carbinols derived from cyclopropyl aryl ketone were evidenced to be superiorer in controlling the stereoselectivity of the products than the alkyl equivalents.
Allylsilanes have emerged as synthetically useful intermediates that can undergo a variety of chemical transformations and have been found versatile applications in C-C bond construction as well as in preparation of complex molecules. Exploration on the stereoselective route to functionalized allylsilanes is of great significance for the development of organic synthetic methodology. An efficient pathway to a series of novel alkoxy-substituted homoiodio-allylsilanes via the Julia olefination of silylmethyl cyclopropyl carbinols was described. Carbinols derived from cyclopropyl aryl ketone were evidenced to be superiorer in controlling the stereoselectivity of the products than the alkyl equivalents.
2019, 39(12): 3460-3466
doi: 10.6023/cjoc201906019
Abstract:
A new thermally activated delayed fluorescence (TADF) acceptor (A) segment, acenaphtho[1, 2-b]quinoxaline (AQ) group, is designed. And a novel red TADF material 10, 10', 10''-(acenaphtho[1, 2-b]quinoxaline-3, 9, 10-triyl)tris(10H-phenoxazine) (AQ-TPXZ) is developed by the conjunction of AQ group with phenoxazine as donor (D) moieties. The density functional theory calculation shows that this D-A molecule has a well separation between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. And the energy splitting between the lowest singlet state and the lowest triplet state is calculated to be 0.02 eV. The transient photoluminescence decays of AQ-TPXZ doped 4, 4'-di(9H-carbazol-9-yl)-1, 1'-biphenyl film exhibit double-component emission decay profiles. The organic light-emitting diode (OLED) using AQ-TPXZ as dopant realizes red emission with a peak at 624 nm. Moreover, the device obtains maximum external quantum efficiency (EQE) up to 7.4%, which is higher than the theoretical maximum EQE (5%) of traditional fluorescent OLEDs. This result not only indicates that AQ-TPXZ is a red TADF material but also provides a newly electron acceptor segment for designing novel red TADF emitters.
A new thermally activated delayed fluorescence (TADF) acceptor (A) segment, acenaphtho[1, 2-b]quinoxaline (AQ) group, is designed. And a novel red TADF material 10, 10', 10''-(acenaphtho[1, 2-b]quinoxaline-3, 9, 10-triyl)tris(10H-phenoxazine) (AQ-TPXZ) is developed by the conjunction of AQ group with phenoxazine as donor (D) moieties. The density functional theory calculation shows that this D-A molecule has a well separation between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. And the energy splitting between the lowest singlet state and the lowest triplet state is calculated to be 0.02 eV. The transient photoluminescence decays of AQ-TPXZ doped 4, 4'-di(9H-carbazol-9-yl)-1, 1'-biphenyl film exhibit double-component emission decay profiles. The organic light-emitting diode (OLED) using AQ-TPXZ as dopant realizes red emission with a peak at 624 nm. Moreover, the device obtains maximum external quantum efficiency (EQE) up to 7.4%, which is higher than the theoretical maximum EQE (5%) of traditional fluorescent OLEDs. This result not only indicates that AQ-TPXZ is a red TADF material but also provides a newly electron acceptor segment for designing novel red TADF emitters.
2019, 39(12): 3475-3482
doi: 10.6023/cjoc201905051
Abstract:
The synthesis of α, α, α-iodo-difluoromethyl alcohols via the high selective reduction of iododifluoromethyl ketones by NaBH4 in methanol at 0℃ was reported. The reaction has some advantages, such as mild condition, simple synthetic route, and high yield. A convenient way to synthesize more difluoromethylation agents was provided.
The synthesis of α, α, α-iodo-difluoromethyl alcohols via the high selective reduction of iododifluoromethyl ketones by NaBH4 in methanol at 0℃ was reported. The reaction has some advantages, such as mild condition, simple synthetic route, and high yield. A convenient way to synthesize more difluoromethylation agents was provided.
2019, 39(12): 3483-3489
doi: 10.6023/cjoc201906006
Abstract:
A series of pillar[5]arene monoamide derivatives with different lengths of alkylenediamine unites as the side chains on the pillar[5]arene's rim can form pseudo[1]rotaxanes. Thus, based on the construction of this intermediate of pseudo[1]rotaxane, eight pillar[5]arene-baed mechanically interlocked molecules (MIMs) of bis-[1]rotaxane were successful constructed through condensation reaction of pillar[5]arene monoamide derivative and salicylaldehyde. The newly synthesized bis-[1]rotaxane was investigated in detail by various methods, including 1H NMR, 13C NMR, 2D NOESY NMR and MS analysis. It was found that this kind of MIMs has a strong recognition effect with Cu2+, which complexed by 1:2.
A series of pillar[5]arene monoamide derivatives with different lengths of alkylenediamine unites as the side chains on the pillar[5]arene's rim can form pseudo[1]rotaxanes. Thus, based on the construction of this intermediate of pseudo[1]rotaxane, eight pillar[5]arene-baed mechanically interlocked molecules (MIMs) of bis-[1]rotaxane were successful constructed through condensation reaction of pillar[5]arene monoamide derivative and salicylaldehyde. The newly synthesized bis-[1]rotaxane was investigated in detail by various methods, including 1H NMR, 13C NMR, 2D NOESY NMR and MS analysis. It was found that this kind of MIMs has a strong recognition effect with Cu2+, which complexed by 1:2.
2019, 39(12): 3490-3497
doi: 10.6023/cjoc201906008
Abstract:
Based on the resistance of glycosidase to the hydrolysis of glycosidase, the probe molecule p-nitrophenyl N, N'-diacetyl-4-thio-β-chitobioside (pNP-TCB) was designed and synthesized. The effects of pNP-TCB on the degradation of glycoside hydrolase family 18 (GH18) chitinase and 20 (GH20) β-N-acetylhexosaminidase were studied. The results showed that when pNP-TCB was combined with β-N-acetylhexosaminidase, the disaccharide substrate was hardly degraded. But when it reacted with chitinase, the pNP-TCB was degraded by enzyme to release p-nitrophenol group, and the corresponding ultraviolet absorption value can be detected by enzyme-labeled instrument at 405 nm. It indicates that the substrate molecule exhibits good specificity, which can be used to study the properties of GH18 chitinase at the cellular level without interference of β-N-acetylhexosaminidase. The pNP-TCB can also provide a good detection method for screening and isolation between the GH18 chitinase and the GH20 β-N-acetyl hexose.
Based on the resistance of glycosidase to the hydrolysis of glycosidase, the probe molecule p-nitrophenyl N, N'-diacetyl-4-thio-β-chitobioside (pNP-TCB) was designed and synthesized. The effects of pNP-TCB on the degradation of glycoside hydrolase family 18 (GH18) chitinase and 20 (GH20) β-N-acetylhexosaminidase were studied. The results showed that when pNP-TCB was combined with β-N-acetylhexosaminidase, the disaccharide substrate was hardly degraded. But when it reacted with chitinase, the pNP-TCB was degraded by enzyme to release p-nitrophenol group, and the corresponding ultraviolet absorption value can be detected by enzyme-labeled instrument at 405 nm. It indicates that the substrate molecule exhibits good specificity, which can be used to study the properties of GH18 chitinase at the cellular level without interference of β-N-acetylhexosaminidase. The pNP-TCB can also provide a good detection method for screening and isolation between the GH18 chitinase and the GH20 β-N-acetyl hexose.
2019, 39(12): 3498-3504
doi: 10.6023/cjoc201906004
Abstract:
An "off-on" fluorescent probe CO-NBS based coumarin derivative was designed and synthesized, which can respond selectively with biothiols including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH). The optical properties were studied by UV-Vis absorption spectrum and fluorescence spectrum. The results showed that probe was capable to respond rapidly, sensitively and selectively to Cys, Hcy and GSH with the detection limits of 92, 30 and 62 nmol/L, respectively. In addition, with low cytotoxicity and good biocompatibility, the probe can be successfully applied to image biothiols in living cells and in living zebrafish.
An "off-on" fluorescent probe CO-NBS based coumarin derivative was designed and synthesized, which can respond selectively with biothiols including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH). The optical properties were studied by UV-Vis absorption spectrum and fluorescence spectrum. The results showed that probe was capable to respond rapidly, sensitively and selectively to Cys, Hcy and GSH with the detection limits of 92, 30 and 62 nmol/L, respectively. In addition, with low cytotoxicity and good biocompatibility, the probe can be successfully applied to image biothiols in living cells and in living zebrafish.
2019, 39(12): 3516-3523
doi: 10.6023/cjoc201904026
Abstract:
12 novel substituted 3, 4-diethoxycarbonyl-2-(thiazol-2-yl)benzo[b] [1, 4]diazepines were obtained via a domino sequence of a nucleophilic addition/dehydration/cyclization/H+ shift. These reactions were achieved by reacting substituted 1, 2-phenylenediamines, 2-thiazolecarboxaldehyde with diethyl acetylenedicarboxylate in EtOH. Benzo[b]-[1, 4]diazepines of the two structures of imine structure and enamine structure were found in this reaction process due to chem-/regio-selectivity. The influence of reaction conditions on the selectivity of target products was also studied in detail. The selectivity law of synthesis reaction was obtained, and the yield of single product was maximized. A simple synthesis strategy for the selective synthesis of benzo[b] [1, 4]diazepines was provided. To understand the reaction mechanism and further prove the conclusion, quantum chemical calculations were performed, and density functional theory (DFT) studies based on B3LYP method and 6-31G basis set were employed to carry out the study. Natural bond orbital (NBO) charge analysis of the substituted 1, 2-phenylenediamine was carried out to justify the selective attack at the nucleophilic centers. NBO charge analysis of the target compounds was carried out to explain the stability of benzo[b] [1, 4]diazepine isomers with imine or enamine structure. Moreover, the plausible reaction mechanism was proposed.
12 novel substituted 3, 4-diethoxycarbonyl-2-(thiazol-2-yl)benzo[b] [1, 4]diazepines were obtained via a domino sequence of a nucleophilic addition/dehydration/cyclization/H+ shift. These reactions were achieved by reacting substituted 1, 2-phenylenediamines, 2-thiazolecarboxaldehyde with diethyl acetylenedicarboxylate in EtOH. Benzo[b]-[1, 4]diazepines of the two structures of imine structure and enamine structure were found in this reaction process due to chem-/regio-selectivity. The influence of reaction conditions on the selectivity of target products was also studied in detail. The selectivity law of synthesis reaction was obtained, and the yield of single product was maximized. A simple synthesis strategy for the selective synthesis of benzo[b] [1, 4]diazepines was provided. To understand the reaction mechanism and further prove the conclusion, quantum chemical calculations were performed, and density functional theory (DFT) studies based on B3LYP method and 6-31G basis set were employed to carry out the study. Natural bond orbital (NBO) charge analysis of the substituted 1, 2-phenylenediamine was carried out to justify the selective attack at the nucleophilic centers. NBO charge analysis of the target compounds was carried out to explain the stability of benzo[b] [1, 4]diazepine isomers with imine or enamine structure. Moreover, the plausible reaction mechanism was proposed.
2019, 39(12): 3532-3541
doi: 10.6023/cjoc201905029
Abstract:
Fifteen novel isosteviol derivatives were designed and synthesized by introducing morpholine and piperazine moieties into C-16 and C-19 position through connecting fragments, and the D-ring structure was modified. The inhibitory effects on Colo-16 and A549 were observed, the results showed that the inhibitory activities of 4 compounds on Colo-16 were significantly better than the positive control of 5-fluorouracil. The inhibitory effects on E. coli 1924, S. aureus 4220, S. mutans 3289, MRSA 3167 and QRSA 3505 were also observed, the results showed that the minimum inhibitory concentration (MIC) of 6 compounds on S. mutans 3289 was 8 μg/mL, which was comparable to the positive control chloramphenicol. The MIC of 16β-O-(5-oxo-5-(4-methyl-1-piperazinyl)-valeryl)]-19-beyeran acid ethyl ester (IS-12b) on MRSA 3167 was 8 μg/mL, which was comparable to the positive control chloramphenicol.
Fifteen novel isosteviol derivatives were designed and synthesized by introducing morpholine and piperazine moieties into C-16 and C-19 position through connecting fragments, and the D-ring structure was modified. The inhibitory effects on Colo-16 and A549 were observed, the results showed that the inhibitory activities of 4 compounds on Colo-16 were significantly better than the positive control of 5-fluorouracil. The inhibitory effects on E. coli 1924, S. aureus 4220, S. mutans 3289, MRSA 3167 and QRSA 3505 were also observed, the results showed that the minimum inhibitory concentration (MIC) of 6 compounds on S. mutans 3289 was 8 μg/mL, which was comparable to the positive control chloramphenicol. The MIC of 16β-O-(5-oxo-5-(4-methyl-1-piperazinyl)-valeryl)]-19-beyeran acid ethyl ester (IS-12b) on MRSA 3167 was 8 μg/mL, which was comparable to the positive control chloramphenicol.
2019, 39(12): 3542-3549
doi: 10.6023/cjoc201904063
Abstract:
A method for the selective synthesis of o-halothiobenzamide by thiolysis reaction of o-halobenzonitrile with NaHS under the action of CO2 was explored. CO2/H2O/NaHS was used as a buffer system to provide a suitable pH environment, which would make HS- attack the nitrile-based carbon selectively to produce the corresponding o-halothiobenzamide. Moreover, the buffer system also provided the additionally required hydrogen atom for the thiolysis reaction of o-haloben-zonitrile with NaHS. Further studies have found that the CO2/Na2S·9H2O buffer system could also efficiently promote the thiolysis reaction of o-halobenzonitrile to form the corresponding o-halothiobenzamide. This synthetic method could be used to prepare different substituted o-halobenzonitriles, which is a simple, efficient and high atom-economic reaction.
A method for the selective synthesis of o-halothiobenzamide by thiolysis reaction of o-halobenzonitrile with NaHS under the action of CO2 was explored. CO2/H2O/NaHS was used as a buffer system to provide a suitable pH environment, which would make HS- attack the nitrile-based carbon selectively to produce the corresponding o-halothiobenzamide. Moreover, the buffer system also provided the additionally required hydrogen atom for the thiolysis reaction of o-haloben-zonitrile with NaHS. Further studies have found that the CO2/Na2S·9H2O buffer system could also efficiently promote the thiolysis reaction of o-halobenzonitrile to form the corresponding o-halothiobenzamide. This synthetic method could be used to prepare different substituted o-halobenzonitriles, which is a simple, efficient and high atom-economic reaction.
2019, 39(12): 3550-3559
doi: 10.6023/cjoc201905009
Abstract:
2, 8-Dioxabicyclo[3.3.1]nonane exists in many natural biologically active materials. Cationic aluminum complex[AlCl(CH3CN)5]2+[(AlCl4)2]2-·CH3CN can be easily prepared via the reaction of AlCl3 with CH3CN at room temperature. It served as efficient catalyst for the tandem Friedel-Crafts alkylation/ketalization reaction of 2-hydroxychalcones with naphthols to produce diaryl-fused 2, 8-dioxabicyclo[3.3.1]nonanes in moderate to high yields. This method provides a practical process to afford this type of biologically important compounds in good yields using easily available and inexpensive catalyst.
2, 8-Dioxabicyclo[3.3.1]nonane exists in many natural biologically active materials. Cationic aluminum complex[AlCl(CH3CN)5]2+[(AlCl4)2]2-·CH3CN can be easily prepared via the reaction of AlCl3 with CH3CN at room temperature. It served as efficient catalyst for the tandem Friedel-Crafts alkylation/ketalization reaction of 2-hydroxychalcones with naphthols to produce diaryl-fused 2, 8-dioxabicyclo[3.3.1]nonanes in moderate to high yields. This method provides a practical process to afford this type of biologically important compounds in good yields using easily available and inexpensive catalyst.
Synthesis of 3-Hydroxy-3-heterocyclebutylamide Derivatives Using Carbamoylsilanes as an Amide Source
2019, 39(12): 3560-3566
doi: 10.6023/cjoc201906033
Abstract:
3-Hydroxy-3-heterocyclebutyl amide derivatives were directly synthesized in 56%~85% yields by nucleophilic addition of various carbamoylsilanes to oxetane-3-one or thietane-3-one in toluene under mild and catalyst-free conditions. This method will provide an efficient route for the synthesis of drugs containing four-membered heterocycles which have not additional stereocentres. The procedure can prepare 3-hydroxy-3-heterocyclebutyl tertiary, secondary and primary amides as well as having a stereocentre connecting with nitrogen atom by selecting different carbamoylsilanes. A comparison of the results obtained from reaction of various carbamoylsilanes indicated that the size of group on the amide group was an important factor in the addition reaction, which influenced on both the reaction time and yields. The reaction has the advantages of mild conditions, less by-products, good yield and simple post-treatment, and is a new method for the efficient preparation of 3-hydroxy-3-heterocycle butylamides.
3-Hydroxy-3-heterocyclebutyl amide derivatives were directly synthesized in 56%~85% yields by nucleophilic addition of various carbamoylsilanes to oxetane-3-one or thietane-3-one in toluene under mild and catalyst-free conditions. This method will provide an efficient route for the synthesis of drugs containing four-membered heterocycles which have not additional stereocentres. The procedure can prepare 3-hydroxy-3-heterocyclebutyl tertiary, secondary and primary amides as well as having a stereocentre connecting with nitrogen atom by selecting different carbamoylsilanes. A comparison of the results obtained from reaction of various carbamoylsilanes indicated that the size of group on the amide group was an important factor in the addition reaction, which influenced on both the reaction time and yields. The reaction has the advantages of mild conditions, less by-products, good yield and simple post-treatment, and is a new method for the efficient preparation of 3-hydroxy-3-heterocycle butylamides.
2019, 39(12): 3567-3573
doi: 10.6023/cjoc201906012
Abstract:
A protocol for the synthesis of a series of indole-1-carboxamides was reported via the N-arboxamidation of indole derivatives with aryl (alkyl) isocyanates catalyzed by 5.0 mol% cesium hydroxide monohydrate (CsOH·H2O). This method is suitable for different indole derivatives and aryl (alkyl) isocyanates, for giving corresponding products in excellent yields. Compared to the reported methods, this protocol has the advantages of mild reaction conditions, wild functional group tolerance, simple operation and excellent yields. An efficient route to indole-1-carboxamides is previded.
A protocol for the synthesis of a series of indole-1-carboxamides was reported via the N-arboxamidation of indole derivatives with aryl (alkyl) isocyanates catalyzed by 5.0 mol% cesium hydroxide monohydrate (CsOH·H2O). This method is suitable for different indole derivatives and aryl (alkyl) isocyanates, for giving corresponding products in excellent yields. Compared to the reported methods, this protocol has the advantages of mild reaction conditions, wild functional group tolerance, simple operation and excellent yields. An efficient route to indole-1-carboxamides is previded.
2019, 39(12): 3574-3582
doi: 10.6023/cjoc201906017
Abstract:
A series of novel pyrazole-4-carboxamide compounds were designed and synthesized through introducing a tertiary alcohol moiety into the C-3 position of the pyrazole ring based on the chracteristics of pyrazole-4-carboxamide fungicides and natural products with a tertiary alcohol moiety. Their structures were characterized by 1H NMR, 13C NMR, HR-ESI-MS data and X-ray diffraction. The preliminary bioassay results indicated that some of these compounds exhibit certain fungicidal activities against tested phytopathogens at the concentration of 100 µg/mL. N-(2-Fluorophenyl)-3-(1-hydroxycyclohexyl)-1, 5-dimethyl-1H-pyrazole-4-carboxamide (B1) and N-(thiazol-2-yl)-3-(1-hydroxycyclohexyl)-1, 5-dimethyl-1H-pyrazole-4-carbo-xamide (B10) have EC50 values of 76.3 and 71.9 µg/mL against Pythium aphanidermatum. B10 has an EC50 value of 85.4 µg/mL against Phytophthora capsici, respectively.
A series of novel pyrazole-4-carboxamide compounds were designed and synthesized through introducing a tertiary alcohol moiety into the C-3 position of the pyrazole ring based on the chracteristics of pyrazole-4-carboxamide fungicides and natural products with a tertiary alcohol moiety. Their structures were characterized by 1H NMR, 13C NMR, HR-ESI-MS data and X-ray diffraction. The preliminary bioassay results indicated that some of these compounds exhibit certain fungicidal activities against tested phytopathogens at the concentration of 100 µg/mL. N-(2-Fluorophenyl)-3-(1-hydroxycyclohexyl)-1, 5-dimethyl-1H-pyrazole-4-carboxamide (B1) and N-(thiazol-2-yl)-3-(1-hydroxycyclohexyl)-1, 5-dimethyl-1H-pyrazole-4-carbo-xamide (B10) have EC50 values of 76.3 and 71.9 µg/mL against Pythium aphanidermatum. B10 has an EC50 value of 85.4 µg/mL against Phytophthora capsici, respectively.
2019, 39(12): 3583-3587
doi: 10.6023/cjoc201904066
Abstract:
The chemical constituents of Hypericum erectum Thunb were isolated and purified by solvent extraction method, the normal and reverse phase silica gel column chromatography and semi-preparative high performance liquid chromatography. Their structures were elucidated by their physicochemical property and extensive analysis of spectroscopic data. Three new compounds which belong to α-pyranone, flavonoid and aliphatic alcohol respectively, together with 15 known compounds, were isolated from the chloroform extract of H. erectum. Inflammatory cell model was constructed by lipopolysaccharide (LPS)-stimulated RAW264.7 cell line. NO production inhibitory effects of all tested compounds were measured by Griess method. Hyperiflavone (2), isocudraniaxan-thone B (5) and 2-deprenylrheediaxanthone B (6) exhibited moderate NO production inhibitory activities with the IC50 values of 16.24, 9.86 and 12.90 μmol·L-1, respectively.
The chemical constituents of Hypericum erectum Thunb were isolated and purified by solvent extraction method, the normal and reverse phase silica gel column chromatography and semi-preparative high performance liquid chromatography. Their structures were elucidated by their physicochemical property and extensive analysis of spectroscopic data. Three new compounds which belong to α-pyranone, flavonoid and aliphatic alcohol respectively, together with 15 known compounds, were isolated from the chloroform extract of H. erectum. Inflammatory cell model was constructed by lipopolysaccharide (LPS)-stimulated RAW264.7 cell line. NO production inhibitory effects of all tested compounds were measured by Griess method. Hyperiflavone (2), isocudraniaxan-thone B (5) and 2-deprenylrheediaxanthone B (6) exhibited moderate NO production inhibitory activities with the IC50 values of 16.24, 9.86 and 12.90 μmol·L-1, respectively.
2019, 39(12): 3588-3593
doi: 10.6023/cjoc201905028
Abstract:
In order to find pesticidal lead compounds with high herbicidal activity, a series of novel chiral aryloxyphenoxypropionic amides were designed and synthesized using the principle of active substructure combination and the technology of biological enzyme splitting. The structures of the target compounds were confirmed by 1H NMR and HRMS. The preliminary bioassay data showed that all target compounds displayed excellent herbicidal activity and selectivity against monocotyledonous weeds. At the dosage of 150 g/ha, the target compounds showed herbicidal activity against Backmannia syzigachne, Polypogon fugax and Poa acroleuca with more than 75%. And the control effects of three compounds against Polypogon fugax Nees were 100%.
In order to find pesticidal lead compounds with high herbicidal activity, a series of novel chiral aryloxyphenoxypropionic amides were designed and synthesized using the principle of active substructure combination and the technology of biological enzyme splitting. The structures of the target compounds were confirmed by 1H NMR and HRMS. The preliminary bioassay data showed that all target compounds displayed excellent herbicidal activity and selectivity against monocotyledonous weeds. At the dosage of 150 g/ha, the target compounds showed herbicidal activity against Backmannia syzigachne, Polypogon fugax and Poa acroleuca with more than 75%. And the control effects of three compounds against Polypogon fugax Nees were 100%.
2019, 39(12): 3594-3595
doi: 10.6023/cjoc201900002
Abstract:
2019, 39(12): 3596-3597
doi: 10.6023/cjoc201900007
Abstract:
2019, 39(12): 3598-3599
doi: 10.6023/cjoc201900008
Abstract:
2019, 39(12): 3600-3601
doi: 10.6023/cjoc201900009
Abstract:
2019, 39(12): 3602-3603
doi: 10.6023/cjoc201900010
Abstract:
