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2016 Volume 36 Issue 2
2016, 36(2): 239-247
doi: 10.6023/cjoc201512006
Abstract:
Synthesis of polysubstituted (hetero)aromatic compounds enabled by visible-light-promoted radical triple bond insertions has been reviewed. A series of polysubstituted naphthols, furans and isoquinolones were prepared using radical alkyne insertions. 6-Substituted phenanthridine and 1-substituted isoquinoline and pyridine derivatives were synthesized assisted by radical isocyanide insertions. Furthermore, a wide scope of quinoline and quinoxaline derivatives were synthesized assisted by domino radical isocyanide/alkyne insertions and isocyanide/cyano insertions respectively. All reactions could be carried out under visible light photoredox catalysis with good to excellent chemical yields.
Synthesis of polysubstituted (hetero)aromatic compounds enabled by visible-light-promoted radical triple bond insertions has been reviewed. A series of polysubstituted naphthols, furans and isoquinolones were prepared using radical alkyne insertions. 6-Substituted phenanthridine and 1-substituted isoquinoline and pyridine derivatives were synthesized assisted by radical isocyanide insertions. Furthermore, a wide scope of quinoline and quinoxaline derivatives were synthesized assisted by domino radical isocyanide/alkyne insertions and isocyanide/cyano insertions respectively. All reactions could be carried out under visible light photoredox catalysis with good to excellent chemical yields.
2016, 36(2): 248-257
doi: 10.6023/cjoc201508002
Abstract:
β-Cyclodextrin has been widely applied in the adsorption of environmental pollutants due to its unique characteristics in structure, and its physical and chemical properties. This review describes some new methods and strategies in the immobilization of β-cyclodextrin to construct adsorbents and their application in the adsorption of environmental pollutants, and some absorbent mechanisms are also discussed. The supporters involved mainly include the inorganic materials, organic polymers, and natural polymers. The immobilization of β-cyclodextrin to construct adsorbents can not only make full use of the inherent advantage in the structure of β-cyclodextrin, but also poss the advantage of immobilization, which can enhance the adsorption performance of adsorbents and their retrievabilities, and meanwhile no additional pollution happens during their application. It is very important in the greenization of adsorbent.
β-Cyclodextrin has been widely applied in the adsorption of environmental pollutants due to its unique characteristics in structure, and its physical and chemical properties. This review describes some new methods and strategies in the immobilization of β-cyclodextrin to construct adsorbents and their application in the adsorption of environmental pollutants, and some absorbent mechanisms are also discussed. The supporters involved mainly include the inorganic materials, organic polymers, and natural polymers. The immobilization of β-cyclodextrin to construct adsorbents can not only make full use of the inherent advantage in the structure of β-cyclodextrin, but also poss the advantage of immobilization, which can enhance the adsorption performance of adsorbents and their retrievabilities, and meanwhile no additional pollution happens during their application. It is very important in the greenization of adsorbent.
2016, 36(2): 258-273
doi: 10.6023/cjoc201509030
Abstract:
Carbonyl compounds are key synthetic intermediates in the fields of medicine, pesticide, perfumes and cosmetics. In recent years, transition metal catalyzed isomerization of allylic alcohols to synthesize various carbonyl compounds has drawn much attention and been explored extensively, due to their high atomic economy and unique superiority. The recent development of the isomerization reactions of allylic alcohols catalyzed by various transition metals is summarized.
Carbonyl compounds are key synthetic intermediates in the fields of medicine, pesticide, perfumes and cosmetics. In recent years, transition metal catalyzed isomerization of allylic alcohols to synthesize various carbonyl compounds has drawn much attention and been explored extensively, due to their high atomic economy and unique superiority. The recent development of the isomerization reactions of allylic alcohols catalyzed by various transition metals is summarized.
2016, 36(2): 274-282
doi: 10.6023/cjoc201509016
Abstract:
Phosphoramidites, as a class of privileged chiral ligands, are suitable for different types of reactions, such as catalytic asymmetric hydrogenation, catalytic asymmetric allylic substitution, catalytic asymmetric Diels-Alder reaction and so on. Catalytic asymmetric hydrogenation reactions are some of the most important reactions in industry. In this review recent advances and applications of phosphoramidite ligands in Ir-catalyzed asymmetric hydrogenation of enamides and their derivatives, unfunctionalized enamines, imines and heteroaromatic compounds are discussed.
Phosphoramidites, as a class of privileged chiral ligands, are suitable for different types of reactions, such as catalytic asymmetric hydrogenation, catalytic asymmetric allylic substitution, catalytic asymmetric Diels-Alder reaction and so on. Catalytic asymmetric hydrogenation reactions are some of the most important reactions in industry. In this review recent advances and applications of phosphoramidite ligands in Ir-catalyzed asymmetric hydrogenation of enamides and their derivatives, unfunctionalized enamines, imines and heteroaromatic compounds are discussed.
2016, 36(2): 283-296
doi: 10.6023/cjoc201507001
Abstract:
3,4-Dihydropyrimidinethiones are chiral molecules, however, only racemic products are isolated in the most reported Biginelli reactions. It has been proved that the absolute configuration of the C(4) stereogenic center has significant influence on the biological activity. The development in the accessing of optically active 3,4-dihydropyrimidinethiones focusing on the recent advances in the asymmetric catalytic Biginelli reactions is summarized.
3,4-Dihydropyrimidinethiones are chiral molecules, however, only racemic products are isolated in the most reported Biginelli reactions. It has been proved that the absolute configuration of the C(4) stereogenic center has significant influence on the biological activity. The development in the accessing of optically active 3,4-dihydropyrimidinethiones focusing on the recent advances in the asymmetric catalytic Biginelli reactions is summarized.
2016, 36(2): 297-305
doi: 10.6023/cjoc201508010
Abstract:
Interactions between nicotiamide adenine dinucleotide (NAD+) and NAD+-dependent enzyme play a crucial role in cellular redox state, energy metabolism, catabolism, anabolism and signal transduction. The rules of interaction between NAD+ and NAD+-dependent enzyme have attracted increasing attention due to so many cellular processes are connected to NAD+. This review highlights some recent progresses in the fields of NAD+ analogs synthesis and interactions with NAD+- dependent enzyme including the synthesis of NAD+ analogs and its interactions with wild NAD+-dependent enzyme, interactions between NAD+ and mutant enzymes, interactions between NAD+ analogs and mutant enzymes.
Interactions between nicotiamide adenine dinucleotide (NAD+) and NAD+-dependent enzyme play a crucial role in cellular redox state, energy metabolism, catabolism, anabolism and signal transduction. The rules of interaction between NAD+ and NAD+-dependent enzyme have attracted increasing attention due to so many cellular processes are connected to NAD+. This review highlights some recent progresses in the fields of NAD+ analogs synthesis and interactions with NAD+- dependent enzyme including the synthesis of NAD+ analogs and its interactions with wild NAD+-dependent enzyme, interactions between NAD+ and mutant enzymes, interactions between NAD+ analogs and mutant enzymes.
2016, 36(2): 306-314
doi: 10.6023/cjoc201508029
Abstract:
Chiral bifunctional (thio)ureas, which are made up of (thio)urea group, nucleophilic activation group and auxiliary, have attracted widespread attention in asymmetric organocatalysis research nowadays because of their easy control structure and excellent catalytic performance. The introduction of the activation group, which can greatly influence the catalytic performance of the catalyst, has become an important and concern research field for the catalyst design, while the introduction of suitable auxiliary can also be used to control and optimize catalytic performance, and become an important supplementary method. However, up to now, there is no systematical review exclusively on utilization of auxiliary strategy for the construction of chiral bifunctional (thio)ureas. In this paper, the research progress of the construction of chiral bifunctional (thio)ureas based on tunable achiral and chiral auxiliaries in recent years is reviewed. These catalysts can be successfully applied in a diverse variety of highly enantioselective transformations providing a wide range of versatile organic compounds. The influence of several factors in the auxiliaries, such as steric hindrance, chiral environment, electronic effect and hydrogen bond donor, on the catalytic performance is described. Besides, an outlook for future development of auxiliaries to construct bifunctional (thio)ureas is given.
Chiral bifunctional (thio)ureas, which are made up of (thio)urea group, nucleophilic activation group and auxiliary, have attracted widespread attention in asymmetric organocatalysis research nowadays because of their easy control structure and excellent catalytic performance. The introduction of the activation group, which can greatly influence the catalytic performance of the catalyst, has become an important and concern research field for the catalyst design, while the introduction of suitable auxiliary can also be used to control and optimize catalytic performance, and become an important supplementary method. However, up to now, there is no systematical review exclusively on utilization of auxiliary strategy for the construction of chiral bifunctional (thio)ureas. In this paper, the research progress of the construction of chiral bifunctional (thio)ureas based on tunable achiral and chiral auxiliaries in recent years is reviewed. These catalysts can be successfully applied in a diverse variety of highly enantioselective transformations providing a wide range of versatile organic compounds. The influence of several factors in the auxiliaries, such as steric hindrance, chiral environment, electronic effect and hydrogen bond donor, on the catalytic performance is described. Besides, an outlook for future development of auxiliaries to construct bifunctional (thio)ureas is given.
2016, 36(2): 306-314
doi: 10.6023/cjoc201508029
Abstract:
Chiral bifunctional (thio)ureas, which are made up of (thio)urea group, nucleophilic activation group and auxiliary, have attracted widespread attention in asymmetric organocatalysis research nowadays because of their easy control structure and excellent catalytic performance. The introduction of the activation group, which can greatly influence the catalytic performance of the catalyst, has become an important and concern research field for the catalyst design, while the introduction of suitable auxiliary can also be used to control and optimize catalytic performance, and become an important supplementary method. However, up to now, there is no systematical review exclusively on utilization of auxiliary strategy for the construction of chiral bifunctional (thio)ureas. In this paper, the research progress of the construction of chiral bifunctional (thio)ureas based on tunable achiral and chiral auxiliaries in recent years is reviewed. These catalysts can be successfully applied in a diverse variety of highly enantioselective transformations providing a wide range of versatile organic compounds. The influence of several factors in the auxiliaries, such as steric hindrance, chiral environment, electronic effect and hydrogen bond donor, on the catalytic performance is described. Besides, an outlook for future development of auxiliaries to construct bifunctional (thio)ureas is given.
Chiral bifunctional (thio)ureas, which are made up of (thio)urea group, nucleophilic activation group and auxiliary, have attracted widespread attention in asymmetric organocatalysis research nowadays because of their easy control structure and excellent catalytic performance. The introduction of the activation group, which can greatly influence the catalytic performance of the catalyst, has become an important and concern research field for the catalyst design, while the introduction of suitable auxiliary can also be used to control and optimize catalytic performance, and become an important supplementary method. However, up to now, there is no systematical review exclusively on utilization of auxiliary strategy for the construction of chiral bifunctional (thio)ureas. In this paper, the research progress of the construction of chiral bifunctional (thio)ureas based on tunable achiral and chiral auxiliaries in recent years is reviewed. These catalysts can be successfully applied in a diverse variety of highly enantioselective transformations providing a wide range of versatile organic compounds. The influence of several factors in the auxiliaries, such as steric hindrance, chiral environment, electronic effect and hydrogen bond donor, on the catalytic performance is described. Besides, an outlook for future development of auxiliaries to construct bifunctional (thio)ureas is given.
2016, 36(2): 315-324
doi: 10.6023/cjoc201512015
Abstract:
In this paper, the enantioselective total synthesis and structure revision of the proposed structure of isochaetominine 8 are described. On the basis of the stereodivergent strategy, a highly efficient five-step synthesis of the proposed structure of isochaetominine 8 and its diastereomer (+)-2,3,14-tri-epi-chaetominine (12) was achieved. The method features the use of L-tryptophan and L-alanine benzyl ester as the starting materials, and a dimethyldioxirane (DMDO)-triggered tandem reaction as a key step. A comparison of the physical and spectral data of the natural isochaetominine with those of the diastereomers obtained during our previous stereodivergent synthesis of chaetominine (1), allowed revising the structure of isochaetominine as (－)-11-epi-chaetominine (18). The first enantioselective total synthesis of this natural product has been accomplished previously in our laboratories in five steps, 31.6% overall yield from L-tryptophan. Besides, an investigation on the L-tryptophan and L-valine tert-butyl ester-based synthesis of isochaetominine C resulted in a stereodivergent synthesis of three diastereomers of isochaetominine C. Finally, it was revealed that attempted site selective epimerization at C(14) of 13B led to a bis-epimerization at both C(14) and C(11).
In this paper, the enantioselective total synthesis and structure revision of the proposed structure of isochaetominine 8 are described. On the basis of the stereodivergent strategy, a highly efficient five-step synthesis of the proposed structure of isochaetominine 8 and its diastereomer (+)-2,3,14-tri-epi-chaetominine (12) was achieved. The method features the use of L-tryptophan and L-alanine benzyl ester as the starting materials, and a dimethyldioxirane (DMDO)-triggered tandem reaction as a key step. A comparison of the physical and spectral data of the natural isochaetominine with those of the diastereomers obtained during our previous stereodivergent synthesis of chaetominine (1), allowed revising the structure of isochaetominine as (－)-11-epi-chaetominine (18). The first enantioselective total synthesis of this natural product has been accomplished previously in our laboratories in five steps, 31.6% overall yield from L-tryptophan. Besides, an investigation on the L-tryptophan and L-valine tert-butyl ester-based synthesis of isochaetominine C resulted in a stereodivergent synthesis of three diastereomers of isochaetominine C. Finally, it was revealed that attempted site selective epimerization at C(14) of 13B led to a bis-epimerization at both C(14) and C(11).
2016, 36(2): 325-329
doi: 10.6023/cjoc201509008
Abstract:
A simple and metal-free radical addition/cyclization reaction of N-aryl acrylamides with CHCl3 or CH2Cl2 as radical source in the presence of benzoyl peroxide (BPO) as oxidant is developed, which affords polychloromethylated 2-oxindoles in moderate to good yields.
A simple and metal-free radical addition/cyclization reaction of N-aryl acrylamides with CHCl3 or CH2Cl2 as radical source in the presence of benzoyl peroxide (BPO) as oxidant is developed, which affords polychloromethylated 2-oxindoles in moderate to good yields.
2016, 36(2): 330-335
doi: 10.6023/cjoc201509044
Abstract:
3-Unsubstituted indolizine not only exhibits a variety of important biological activities, but also is a kind of important intermediate in organic synthesis. A transition metal free method for synthesizing 3-unsubstituted indolizines from pyridines, 2-chloroacetic acid and electron deficient alkenes has been invented in this paper. The designed products were obtained via oxidative dehydrogenation and decarboxylation reactions, and 2,2,6,6-tetramthyl-1-piperidinyloxy (TEMPO) was used as an oxidant. This method featured simple procedure, easy available starting materials and transition metal free conditions.
3-Unsubstituted indolizine not only exhibits a variety of important biological activities, but also is a kind of important intermediate in organic synthesis. A transition metal free method for synthesizing 3-unsubstituted indolizines from pyridines, 2-chloroacetic acid and electron deficient alkenes has been invented in this paper. The designed products were obtained via oxidative dehydrogenation and decarboxylation reactions, and 2,2,6,6-tetramthyl-1-piperidinyloxy (TEMPO) was used as an oxidant. This method featured simple procedure, easy available starting materials and transition metal free conditions.
2016, 36(2): 336-345
doi: 10.6023/cjoc201508023
Abstract:
Λ-shaped geometry configuration of Tröger's base (TB) is theoretically disadvantages to form π-π close stacking, which commonly results in fluorescence quenching in the solid state. A number of Λ-shaped cyano styrene based on Tröger's base (compounds 1a, 2a, 3a and 4a) was firstly developed with the structure of D-π-C-π-D which exhibited a typical aggregation-induced emission (AIE) behavior via Knoevenagel reaction with high yield. The thiophene ring was successful introduced into the Tröger's base skeleton firstly to obtain novel compound 5a with good solid luminescence via palladium-catalyzed Heck coupling reaction. The phenyl groups and thiophene ring were used as the electron donor and TB was used as a nucleus. All of these compounds were characterized and confirmed by 1H NMR, 13C NMR and MS spectra. All of the compounds were highly emissive in the condensed phase. In addition, compounds 1a, 2a, 3a and 4a were weakly fluorescent in solutions, but compound 5a exhibited blue emission strongly in solution, which revealed distinct aggregation-induced emission characteristics. The photo-physical properties of these compounds were studied in detail. We aimed at verifying the AIE properties of these compounds mainly. And the results showed a significant increase in fluorescence of these compounds with the addition of water, indicating that the synthesized compounds really have apparent AIE behavior. The solvent effect behavior was investigated to evaluate the effect of the solvent polarity on compounds 1a, 2a and 5a. Compound 2a showed some solvent effect, and all the emission peaks were red-shifted due to the increasing of the polarity of the solvents, indicating that a significant ICT effect existed in these compounds. In summary, in the process of the exploration of highly emissive organic solids, a new design strategy was presented and a new system of AIE materials was established. This study reveals that when constructing aggregation-induced emission molecules using substituent groups with expanded π-conjugation and introduction of appropriate steric hindrance on the substituent groups can restrict the formation of excimers effectively, hence achieving efficient solid state emission, which are expected to be used in electroluminescent field with potential value.
Λ-shaped geometry configuration of Tröger's base (TB) is theoretically disadvantages to form π-π close stacking, which commonly results in fluorescence quenching in the solid state. A number of Λ-shaped cyano styrene based on Tröger's base (compounds 1a, 2a, 3a and 4a) was firstly developed with the structure of D-π-C-π-D which exhibited a typical aggregation-induced emission (AIE) behavior via Knoevenagel reaction with high yield. The thiophene ring was successful introduced into the Tröger's base skeleton firstly to obtain novel compound 5a with good solid luminescence via palladium-catalyzed Heck coupling reaction. The phenyl groups and thiophene ring were used as the electron donor and TB was used as a nucleus. All of these compounds were characterized and confirmed by 1H NMR, 13C NMR and MS spectra. All of the compounds were highly emissive in the condensed phase. In addition, compounds 1a, 2a, 3a and 4a were weakly fluorescent in solutions, but compound 5a exhibited blue emission strongly in solution, which revealed distinct aggregation-induced emission characteristics. The photo-physical properties of these compounds were studied in detail. We aimed at verifying the AIE properties of these compounds mainly. And the results showed a significant increase in fluorescence of these compounds with the addition of water, indicating that the synthesized compounds really have apparent AIE behavior. The solvent effect behavior was investigated to evaluate the effect of the solvent polarity on compounds 1a, 2a and 5a. Compound 2a showed some solvent effect, and all the emission peaks were red-shifted due to the increasing of the polarity of the solvents, indicating that a significant ICT effect existed in these compounds. In summary, in the process of the exploration of highly emissive organic solids, a new design strategy was presented and a new system of AIE materials was established. This study reveals that when constructing aggregation-induced emission molecules using substituent groups with expanded π-conjugation and introduction of appropriate steric hindrance on the substituent groups can restrict the formation of excimers effectively, hence achieving efficient solid state emission, which are expected to be used in electroluminescent field with potential value.
2016, 36(2): 346-351
doi: 10.6023/cjoc201509007
Abstract:
Two series of porphyrins and their Zn (II) complexes modified with long chain alkylferrocene were designed. One was close conjugate connection of porphyrin and ferrocene containing long chain alkyl group by an amide linkage in meso site of porphyrin (porphyrin 5 and its Zn (II) complex 6), the other was placed ferrocene on the skirt of meso-tetraphenylporphyrin with long chain alkoxy group (porphyrin 7 and its Zn(II) complex 8). The spectroscopic and electrochemistry properties of two series of compounds were investigated. The absorption bands of free porphyrins were almost the same, but those of their Zn(II) complexes were red-shifted by 7 nm. Porphyrins 5 and 6 with an amide linkage exhibited strong fluorescence quenching with a low quantum yield compared with those containing a long chain alkoxy group linkage (7 and 8). Compared with the free porphyrins, the negative potential shifts of the Zn(II) complexes were observed in cyclic voltammetry experiments. In addition, the first oxidation potentials of porphyrin in 7 and 8 were slight negative shifts relative to 5 and 6, but the first oxidation potentials of ferrocene in 7 and 8 shifted about 182～194 mV.
Two series of porphyrins and their Zn (II) complexes modified with long chain alkylferrocene were designed. One was close conjugate connection of porphyrin and ferrocene containing long chain alkyl group by an amide linkage in meso site of porphyrin (porphyrin 5 and its Zn (II) complex 6), the other was placed ferrocene on the skirt of meso-tetraphenylporphyrin with long chain alkoxy group (porphyrin 7 and its Zn(II) complex 8). The spectroscopic and electrochemistry properties of two series of compounds were investigated. The absorption bands of free porphyrins were almost the same, but those of their Zn(II) complexes were red-shifted by 7 nm. Porphyrins 5 and 6 with an amide linkage exhibited strong fluorescence quenching with a low quantum yield compared with those containing a long chain alkoxy group linkage (7 and 8). Compared with the free porphyrins, the negative potential shifts of the Zn(II) complexes were observed in cyclic voltammetry experiments. In addition, the first oxidation potentials of porphyrin in 7 and 8 were slight negative shifts relative to 5 and 6, but the first oxidation potentials of ferrocene in 7 and 8 shifted about 182～194 mV.
2016, 36(2): 352-357
doi: 10.6023/cjoc201509026
Abstract:
The reaction of the thiolazole compounds with aryl iodide resulted in a series of aryl thioether compounds under microwave irradiation. It showed that the yield of target product was 88% when the reaction was carried out under microwave (30 W) heating for 15 min in N,N-dimethylformamide (DMF). The target products using microwave response and oil bath heating were tracked separately by high performance liquid chromatography (HPLC) analysis under the same conditions. The results showed that the method of microwave irradiation for the preparation of aryl sulfide was simple, efficient, time-saving and less by-products. It is expected to become an efficient, gentle and environmentally friendly synthetic method of heterocyclic aryl sulfides.
The reaction of the thiolazole compounds with aryl iodide resulted in a series of aryl thioether compounds under microwave irradiation. It showed that the yield of target product was 88% when the reaction was carried out under microwave (30 W) heating for 15 min in N,N-dimethylformamide (DMF). The target products using microwave response and oil bath heating were tracked separately by high performance liquid chromatography (HPLC) analysis under the same conditions. The results showed that the method of microwave irradiation for the preparation of aryl sulfide was simple, efficient, time-saving and less by-products. It is expected to become an efficient, gentle and environmentally friendly synthetic method of heterocyclic aryl sulfides.
2016, 36(2): 358-362
doi: 10.6023/cjoc201507029
Abstract:
15 Schiff bases were synthesized by the reactions of 3-p-chlorophenyl, 3-p-methoxyphenyl and 3-n-pentyl-1,2,4-triazole with five different aromatic aldehydes, respectively. Then 14 novel Mannich bases (PCTABM, PMTABM and PETABM) were first afforded by the reactions of Schiff bases with formaldehyde and morpholine through multi-component one-pot reaction. In order to explore the effect of different 3-substituted groups on biological activities, four Mannich bases FcTABM of 3-ferrocenyl-1,2,4-triazole were also synthesized starting from 3-ferrocenyl-1,2,4-triazole by the similar method. IR, 1H NMR and HRMS were used to characterize the structure of the target molecules. The biological activities of the target molecules were evaluated. As a result, the target compounds exhibited excellent activities in plant growth regulators and herbicidal activity. There are 14 target compounds exhibited excellent inhibitory activity against Cdc25B, in which the IC50 values of 7c, 8e, 9e, 10b～10e IC50 were all smaller than the reference Na3VO4, which were expected to be Cdc25B inhibitors.
15 Schiff bases were synthesized by the reactions of 3-p-chlorophenyl, 3-p-methoxyphenyl and 3-n-pentyl-1,2,4-triazole with five different aromatic aldehydes, respectively. Then 14 novel Mannich bases (PCTABM, PMTABM and PETABM) were first afforded by the reactions of Schiff bases with formaldehyde and morpholine through multi-component one-pot reaction. In order to explore the effect of different 3-substituted groups on biological activities, four Mannich bases FcTABM of 3-ferrocenyl-1,2,4-triazole were also synthesized starting from 3-ferrocenyl-1,2,4-triazole by the similar method. IR, 1H NMR and HRMS were used to characterize the structure of the target molecules. The biological activities of the target molecules were evaluated. As a result, the target compounds exhibited excellent activities in plant growth regulators and herbicidal activity. There are 14 target compounds exhibited excellent inhibitory activity against Cdc25B, in which the IC50 values of 7c, 8e, 9e, 10b～10e IC50 were all smaller than the reference Na3VO4, which were expected to be Cdc25B inhibitors.
2016, 36(2): 364-369
doi: 10.6023/cjoc201505041
Abstract:
A novel methodology has been developed for the synthesis of N-substituted mono-pyrrole and bis-pyrrole derivatives with a chiral substituent at the nitrogen atom by MgI2-catalyzed Paal-Knorr condensation using esters of amino acids as the source of chirality. This method has some advantages such as mild reaction conditions, simple procedure, good yields, high stereoselectivity and environmental friendliness.
A novel methodology has been developed for the synthesis of N-substituted mono-pyrrole and bis-pyrrole derivatives with a chiral substituent at the nitrogen atom by MgI2-catalyzed Paal-Knorr condensation using esters of amino acids as the source of chirality. This method has some advantages such as mild reaction conditions, simple procedure, good yields, high stereoselectivity and environmental friendliness.
2016, 36(2): 370-376
doi: 10.6023/cjoc201509010
Abstract:
This paper reports the selective condensation of aminoguanidine with 1-(1-ethyl-1H-indol-5-yl)-2-phenylethane- 1,2-dione to afford 1,2,4-triazines. The constituents and relative proportion of these condensation products are identified by the methods of target-oriented synthesis and nuclear magnetic resonance. And the influences on the relative proportion by different substituents are described. When the phenyl is substituted with the electron-withdrawing group, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-phenyl-1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-phenyl-1,2,4-triazin-3-amine [n(2a):n(4a)] is 40:60; when without the substituent, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-(4-nitrophenyl)- 1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-(4-nitrophenyl)-1,2,4-triazin-3-amine [n(2b):n(4b)] is 63:37; when substituted with the electron-donating group, the type of the major products was 2.
This paper reports the selective condensation of aminoguanidine with 1-(1-ethyl-1H-indol-5-yl)-2-phenylethane- 1,2-dione to afford 1,2,4-triazines. The constituents and relative proportion of these condensation products are identified by the methods of target-oriented synthesis and nuclear magnetic resonance. And the influences on the relative proportion by different substituents are described. When the phenyl is substituted with the electron-withdrawing group, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-phenyl-1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-phenyl-1,2,4-triazin-3-amine [n(2a):n(4a)] is 40:60; when without the substituent, the ratio of the isomers 6-(1-ethyl-1H-indol-5-yl)-5-(4-nitrophenyl)- 1,2,4-triazin-3-amine/5-(1-ethyl-1H-indol-5-yl)-6-(4-nitrophenyl)-1,2,4-triazin-3-amine [n(2b):n(4b)] is 63:37; when substituted with the electron-donating group, the type of the major products was 2.
2016, 36(2): 377-383
doi: 10.6023/cjoc201510020
Abstract:
In order to find novel pyridine phenyl ether lead compounds, a series of novel pyridine phenyl ether derivatives containing N-heterocycles were prepared by the strategy of active substructure combination. Their structures were determined by 1H NMR, 13C NMR, IR and elemental analysis. Preliminary bioassay data displayed that some of the designed compounds exhibited good insecticidal activity. Additionally, some target compounds showed significant anti-tumor activities.
In order to find novel pyridine phenyl ether lead compounds, a series of novel pyridine phenyl ether derivatives containing N-heterocycles were prepared by the strategy of active substructure combination. Their structures were determined by 1H NMR, 13C NMR, IR and elemental analysis. Preliminary bioassay data displayed that some of the designed compounds exhibited good insecticidal activity. Additionally, some target compounds showed significant anti-tumor activities.
2016, 36(2): 384-392
doi: 10.6023/cjoc201507023
Abstract:
Promoted by activated carbon, novel benzoimidazole derivatives containing indole unit were synthesized via cyclocondensation-oxidation of N-alkylindole-3-formaldehyde with 1,2-diaminobenzene in the presences of atmospheric air as a “green” oxidant. The effects of activated carbon, selection & amount of solvents, temperature and molar ratio of the two reagents on the reactions have been surveyed. UV-Vis and fluorescence spectra of the title compounds in acetonitrile were also investigated.
Promoted by activated carbon, novel benzoimidazole derivatives containing indole unit were synthesized via cyclocondensation-oxidation of N-alkylindole-3-formaldehyde with 1,2-diaminobenzene in the presences of atmospheric air as a “green” oxidant. The effects of activated carbon, selection & amount of solvents, temperature and molar ratio of the two reagents on the reactions have been surveyed. UV-Vis and fluorescence spectra of the title compounds in acetonitrile were also investigated.
2016, 36(2): 393-398
doi: 10.6023/cjoc201509011
Abstract:
In order to find novel triazole lead compounds, a series of new triazole derivatives containing pyridine moiety were synthesized by the introduction of the important pyridyl backbone into the molecules of triazoles. They were structurally confirmed by 1H NMR, 13C NMR, IR, MS and elemental analysis. Additionally, compound 4k was structurally characterized through X-ray single crystal diffraction method. Preliminary bioassay data showed that some of the title compounds displayed moderate fungicidal and plant growth regulatory activities.
In order to find novel triazole lead compounds, a series of new triazole derivatives containing pyridine moiety were synthesized by the introduction of the important pyridyl backbone into the molecules of triazoles. They were structurally confirmed by 1H NMR, 13C NMR, IR, MS and elemental analysis. Additionally, compound 4k was structurally characterized through X-ray single crystal diffraction method. Preliminary bioassay data showed that some of the title compounds displayed moderate fungicidal and plant growth regulatory activities.
2016, 36(2): 399-405
doi: 10.6023/cjoc201509025
Abstract:
2-Cyclohexylcyclododecanone and 2-phenylcyclododecanone were synthesized via reaction of cyclododecanone with bromocyclohexane and lithium phenide using cyclododecanone as raw material, respectivey. The 1,1'-dihydroxy-1,1'- bicyclododecane was also obtained unexpected. 2-Cyclohexylcyclododecanone oxime and 2-phenylcyclododecanone oxime were prepared by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with hydroxylamine chloride, 3-cyclohexylcyclododecan-1,2-dione monooxime and 3-phenyl-cyclododecan-1,2-dione monooxime were synthesized by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with NaNO2-HCl system. Their crystals were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333] conformation was took by the cyclododecane ring of 1-phenylcyclododecanol and 1,1'-dihydroxy-1,1'-bicyclododecane, the two substituted groups were at corner position, while 2-cyclohexylcyclododecanone oxime took [3333]-2-one, 3-phenylcyclododecan-1,2-dione monooxime took [4233]-3,4-dione conformation and the substituted groups were at side-exo position in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction. In the crystal structure of 1,1'-dihydroxy- 1,1'-bicyclododecane, the molecules exhibited unique self-assembly property of complete disc overlapping between two molecular layers in the a-axis direction with intermolecular hydrogen bond.
2-Cyclohexylcyclododecanone and 2-phenylcyclododecanone were synthesized via reaction of cyclododecanone with bromocyclohexane and lithium phenide using cyclododecanone as raw material, respectivey. The 1,1'-dihydroxy-1,1'- bicyclododecane was also obtained unexpected. 2-Cyclohexylcyclododecanone oxime and 2-phenylcyclododecanone oxime were prepared by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with hydroxylamine chloride, 3-cyclohexylcyclododecan-1,2-dione monooxime and 3-phenyl-cyclododecan-1,2-dione monooxime were synthesized by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with NaNO2-HCl system. Their crystals were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333] conformation was took by the cyclododecane ring of 1-phenylcyclododecanol and 1,1'-dihydroxy-1,1'-bicyclododecane, the two substituted groups were at corner position, while 2-cyclohexylcyclododecanone oxime took [3333]-2-one, 3-phenylcyclododecan-1,2-dione monooxime took [4233]-3,4-dione conformation and the substituted groups were at side-exo position in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction. In the crystal structure of 1,1'-dihydroxy- 1,1'-bicyclododecane, the molecules exhibited unique self-assembly property of complete disc overlapping between two molecular layers in the a-axis direction with intermolecular hydrogen bond.
2016, 36(2): 406-411
doi: 10.6023/cjoc201507004
Abstract:
11 novel 1, 3, 4-oxadiazole triazene derivatives were designed and synthesized by combination of triazenes and 1, 3, 4-oxadiazoles. All the target compounds were characterized by 1H NMR, IR and HRMS. The antitumor activities of all compounds were screened by using thiazolylblue (MTT) assay in vitro, in which MGC803 cell lines and PC-3 cell lines were used as the test cancer cell. The results showed that compounds 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(4-methoxy-phenyl)-1, 3, 4-oxadiazole (b4), 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(2-methoxyphenyl)-1, 3, 4-oxadiazole (b9), 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(benzo[d][1, 3]dioxol-5-yl)-1, 3, 4-oxadiazole (b10) and 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(pyridin-4-yl)-1, 3, 4-oxadiazole (b11) exhibited higher activity against PC-3 cell than control compound dacarbazine (DTIC), and their IC50 values were 74.145, 87.790, 87.327 and 104.875 μmol/L, respectively. But all compounds had little inhibition effect on MGC803 cell lines. All synthesized compounds were screened by broth dilution technique for their fungicidal activity against S. aureus and E. coli. The antibacterial activity results showed that all of compounds were inactive.
11 novel 1, 3, 4-oxadiazole triazene derivatives were designed and synthesized by combination of triazenes and 1, 3, 4-oxadiazoles. All the target compounds were characterized by 1H NMR, IR and HRMS. The antitumor activities of all compounds were screened by using thiazolylblue (MTT) assay in vitro, in which MGC803 cell lines and PC-3 cell lines were used as the test cancer cell. The results showed that compounds 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(4-methoxy-phenyl)-1, 3, 4-oxadiazole (b4), 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(2-methoxyphenyl)-1, 3, 4-oxadiazole (b9), 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(benzo[d][1, 3]dioxol-5-yl)-1, 3, 4-oxadiazole (b10) and 2-(4-(3, 3-dimethyltriaz-1-en-1-yl)phenyl)-5-(pyridin-4-yl)-1, 3, 4-oxadiazole (b11) exhibited higher activity against PC-3 cell than control compound dacarbazine (DTIC), and their IC50 values were 74.145, 87.790, 87.327 and 104.875 μmol/L, respectively. But all compounds had little inhibition effect on MGC803 cell lines. All synthesized compounds were screened by broth dilution technique for their fungicidal activity against S. aureus and E. coli. The antibacterial activity results showed that all of compounds were inactive.
2016, 36(2): 412-416
doi: 10.6023/cjoc201509039
Abstract:
Radical polymer poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), a potential cathode materials, was prepared by radical polymerization of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) containing secondary amine group, followed by oxidation into radical polymer. However, the living radical polymerization of TMPM was hindered by its secondary amine group. The optimized atom transfer radical polymerization condition for TMPM via screening various initiators and catalyst systems was reported, and poly(2,2,6,6-tetramethylpiperidin-4-yl methacrylate)s with different molecular weight were prepared.
Radical polymer poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), a potential cathode materials, was prepared by radical polymerization of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) containing secondary amine group, followed by oxidation into radical polymer. However, the living radical polymerization of TMPM was hindered by its secondary amine group. The optimized atom transfer radical polymerization condition for TMPM via screening various initiators and catalyst systems was reported, and poly(2,2,6,6-tetramethylpiperidin-4-yl methacrylate)s with different molecular weight were prepared.
2016, 36(2): 417-424
doi: 10.6023/cjoc201507038
Abstract:
Twenty eight novel 1,3,4-thiadiazole derivatives were synthesized using different phenylacetic acids as the starting material, followed by the reaction of cyclization, coupling, deprotection, and finally introduced different substituted benzenesulfonamides. The structures of all target compounds were identified by 1H NMR, 13C NMR and HRMS. The biological evaluation was performed on PC-3 (prostatic cancer cell), MDA-MB-231 (breast cancer cell) and K562 (chronic myelogenous leukemia cell) by 3-(4,5-dimethylthigal-2-yl)-2,5-(diphenyltetragalium) bromide (MTT) assay. The results suggested that some compounds exhibited good anti-proliferative activities against tumor cell lines. Especially, compounds 6a and 6b showed similar inhibitory activities against K562 cell compared with gossypol.
Twenty eight novel 1,3,4-thiadiazole derivatives were synthesized using different phenylacetic acids as the starting material, followed by the reaction of cyclization, coupling, deprotection, and finally introduced different substituted benzenesulfonamides. The structures of all target compounds were identified by 1H NMR, 13C NMR and HRMS. The biological evaluation was performed on PC-3 (prostatic cancer cell), MDA-MB-231 (breast cancer cell) and K562 (chronic myelogenous leukemia cell) by 3-(4,5-dimethylthigal-2-yl)-2,5-(diphenyltetragalium) bromide (MTT) assay. The results suggested that some compounds exhibited good anti-proliferative activities against tumor cell lines. Especially, compounds 6a and 6b showed similar inhibitory activities against K562 cell compared with gossypol.
2016, 36(2): 425-431
doi: 10.6023/cjoc201508025
Abstract:
This paper developed a new method for the construction of polysubstituted indenes. And a number of multisubstituted indenes have been synthesized from functional o-alkenyl bromobenzenes and alkynes in good yields through palladium-catalyzed annulations in N, N-dimethylformamide (DMF) taking Na2CO3 as base. The methodology tolerates a variety of functional groups with simple reaction conditions and the catalyst can be reused.
This paper developed a new method for the construction of polysubstituted indenes. And a number of multisubstituted indenes have been synthesized from functional o-alkenyl bromobenzenes and alkynes in good yields through palladium-catalyzed annulations in N, N-dimethylformamide (DMF) taking Na2CO3 as base. The methodology tolerates a variety of functional groups with simple reaction conditions and the catalyst can be reused.
2016, 36(2): 432-436
doi: 10.6023/cjoc201508030
Abstract:
Seven novel cyclovirobuxine D derivatives were designed and synthesized by using cyclovirobuxine D as a starting material. All compounds synthesized were confirmed by 1H NMR, HRMS and IR. Preliminary results of anti-anoxia activity indicated that compounds displayed different degrees of activity, among them the compounds with piperazinyl exhibited higher anti-anoxia activity than others.
Seven novel cyclovirobuxine D derivatives were designed and synthesized by using cyclovirobuxine D as a starting material. All compounds synthesized were confirmed by 1H NMR, HRMS and IR. Preliminary results of anti-anoxia activity indicated that compounds displayed different degrees of activity, among them the compounds with piperazinyl exhibited higher anti-anoxia activity than others.
