The use of intramolecular reactions involving palladium/imidazolium salts to synthesize hetero-cyclic compounds is described. Reactivity of phenyl, ethyl and methyl substituents leading to isolation of various isomeri...The use of intramolecular reactions involving palladium/imidazolium salts to synthesize hetero-cyclic compounds is described. Reactivity of phenyl, ethyl and methyl substituents leading to isolation of various isomeric products is also illustrated. Rearrangement of phenyl intermediates to furnish benzoxazoles is also mentioned.展开更多
A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chl...A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chloroformate, glyoxal and thiourea to afford different N and S containing heterocycles. The reaction conditions were compared by conventional heating and microwave irradiation. The structures of the cyclization products were de- termined by analytical and spectroscopic data. All the synthesized compounds were screened for antibacterial activities in vitro.展开更多
The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all ...The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.展开更多
A simple route to synthesize novel fluorinated fused hetero-polycyclic nitrogen systems containing a pyrazolotriazine moiety (5,8,11) have been deduced from cyclization of 2-aminothiocarbonyl-5-arylidene-3-phenyl-1,2,...A simple route to synthesize novel fluorinated fused hetero-polycyclic nitrogen systems containing a pyrazolotriazine moiety (5,8,11) have been deduced from cyclization of 2-aminothiocarbonyl-5-arylidene-3-phenyl-1,2,4-triazin-6(1H)one (2) with diethoxy-phosphine, diethyl carbonate and/or diethyl oxalate in boil THF followed by cyclo condensation with aryl sulfonic acid hydrazide in EtOH/piperidine and finally fluorination with trifluoroethyl acetate. Structures of the products have been established from their elemental analysis and spectral measurements. The antimicrobial activity of the targets has also been evaluated.展开更多
The visible light-driven C2 or C3 amination of indoles without any additives was initiated via electron donor-acceptor (EDA) complex formed by indole and N-aminopyridinium salt.This method was compatible with a wide r...The visible light-driven C2 or C3 amination of indoles without any additives was initiated via electron donor-acceptor (EDA) complex formed by indole and N-aminopyridinium salt.This method was compatible with a wide range of substrates and could proceed smoothly without the addition of any photocatalysts,transition-metal catalysts,or bases.A variety of studies were carried out to examine the presence of EDA complex.展开更多
S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles c...S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities.Herein,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions.Therefore,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran derivatives.Typically,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully prepared.Interestingly,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,respectively.Moreover,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory calculations.Therefore,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.展开更多
Fused polycyclic N-heterocycles are very important scaffolds in biomedicinal chemistry and materials science.Intramolecular alkyne hydroamination is a powerful method for the construction of N-heterocycles.In the last...Fused polycyclic N-heterocycles are very important scaffolds in biomedicinal chemistry and materials science.Intramolecular alkyne hydroamination is a powerful method for the construction of N-heterocycles.In the last two decades,copper-catalyzed domino reactions based on intramolecular alkyne hydroamination has emerged as a robust strategy for assembling various fused polycyclic N-heterocycles.Great progress has been achieved in this area.This short review covers the advances made in copper-catalyzed domino synthesis of fused polycyclic N-heterocycles based on the strategy from 2008 to 2023,and will hopefully serve as an inspiration towards the exploration of new copper-catalyzed versions of the transformation.The domino transformations are introduced and discussed from five aspects according to the different key processes involved in these reactions.展开更多
Comprehensive Summary Benzothiadiazine-1,1-dioxide scaffold is bioactive framework with wild utility and applications.Synthesis of benzothiadiazine-fused isoquinoline derivatives and spiro benzothiadiazine derivatives...Comprehensive Summary Benzothiadiazine-1,1-dioxide scaffold is bioactive framework with wild utility and applications.Synthesis of benzothiadiazine-fused isoquinoline derivatives and spiro benzothiadiazine derivatives through transition metal-catalyzed C—H activation/annulation was reported.3-Phenyl-2H-benzothiadiazine-1,1-dioxide was used as the reaction substrate,and vinylene carbonate and 4-diazopyrazolone were used as the coupling reagents,respectively.This strategy provides straightforward access to complex N-heterocycles in a highly efficient and simple manner.展开更多
文摘The use of intramolecular reactions involving palladium/imidazolium salts to synthesize hetero-cyclic compounds is described. Reactivity of phenyl, ethyl and methyl substituents leading to isolation of various isomeric products is also illustrated. Rearrangement of phenyl intermediates to furnish benzoxazoles is also mentioned.
文摘A convenient synthesis of intermediate 4,5-diamino-3-aryl-l-phenylpyrazoles 4a--4c was reported. The different cyclization reactions were carried out with chalcone, 2-mercaptoacetic acid and p-anisialdehyde, ethyl chloroformate, glyoxal and thiourea to afford different N and S containing heterocycles. The reaction conditions were compared by conventional heating and microwave irradiation. The structures of the cyclization products were de- termined by analytical and spectroscopic data. All the synthesized compounds were screened for antibacterial activities in vitro.
文摘The goal of this brief partly review paper is to summarize the results of the works published over the last few years regarding the origin of the out-of-plane distortions (puckering) of heterocyclic compounds. In all the papers devoted to this problem, it is shown that the instability of planar configurations of heterocyclic molecules leading to symmetry breaking and distortions is induced by the pseudo Jahn-Teller effect (PJTE). Special attention in this work is paid to the mechanism of suppression and enhancement of the PJTE distortions of heterocycles by oxidation, reduction, and chemical substitutions. It is demonstrated that oxidation of 1,4-dithiine containing compounds leads to suppression of the PJTE and to restoration of their planar nuclear configurations. An example of a dibenzo[1,2]dithiine molecule is used to demonstrate the mechanism of enhancement of the PJTE by reduction. It is shown that the reduction of the neutral C12H8S2 molecule up to the dianion (C12H8S2)2- enhances the PJTE, followed by the S-S bond cleavage and significant structural distortions of the system. The change of the PJTE by chemical substitutions, accompanied either by puckering or by planarization of heterocyclic compounds, is discussed using as examples 1,4-ditinine and its S-oxygenated derivatives.
文摘A simple route to synthesize novel fluorinated fused hetero-polycyclic nitrogen systems containing a pyrazolotriazine moiety (5,8,11) have been deduced from cyclization of 2-aminothiocarbonyl-5-arylidene-3-phenyl-1,2,4-triazin-6(1H)one (2) with diethoxy-phosphine, diethyl carbonate and/or diethyl oxalate in boil THF followed by cyclo condensation with aryl sulfonic acid hydrazide in EtOH/piperidine and finally fluorination with trifluoroethyl acetate. Structures of the products have been established from their elemental analysis and spectral measurements. The antimicrobial activity of the targets has also been evaluated.
基金financial support from the National Natural Science Foundation of China(Grant Nos.21901216 and 82074003,82174083)the Funds of Sichuan Science and Technology Program(23NSFSC0862,2021YFSY0041,2021YFH0064 and 2021ZHFP0032)+3 种基金the Opening subject under KF-202204 in the State Key Laboratory of Pharmaceutical Biotechnology,Nanjing University,China,the Fund of Science and Technology Agency of Chengdu(2019-YF09-00049-SN)the research project of the Administration of Traditional Chinese Medicine of Sichuan(2021MS110)the Open Project Program of Irradiation Preservation Technology Key Laboratory of Sichuan Province,Sichuan Institute of Atomic Energy(No.FZBC2020002)the Fundamental Research Funds for the Central Universities(2682020ZT85).
文摘The visible light-driven C2 or C3 amination of indoles without any additives was initiated via electron donor-acceptor (EDA) complex formed by indole and N-aminopyridinium salt.This method was compatible with a wide range of substrates and could proceed smoothly without the addition of any photocatalysts,transition-metal catalysts,or bases.A variety of studies were carried out to examine the presence of EDA complex.
基金supported by the National Key Research and Development Program of China(2018YFA0209401)the National Natural Science Foundation of China(22171053,21733003)the Natural Science Foundation of Shanghai(21zR1409600)。
文摘S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities.Herein,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions.Therefore,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran derivatives.Typically,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully prepared.Interestingly,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,respectively.Moreover,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory calculations.Therefore,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.
基金financial supports from the Natural Science Foundation of Zhejiang Province(LY21B020005)the National Natural Science Foundation of China(21202152).
文摘Fused polycyclic N-heterocycles are very important scaffolds in biomedicinal chemistry and materials science.Intramolecular alkyne hydroamination is a powerful method for the construction of N-heterocycles.In the last two decades,copper-catalyzed domino reactions based on intramolecular alkyne hydroamination has emerged as a robust strategy for assembling various fused polycyclic N-heterocycles.Great progress has been achieved in this area.This short review covers the advances made in copper-catalyzed domino synthesis of fused polycyclic N-heterocycles based on the strategy from 2008 to 2023,and will hopefully serve as an inspiration towards the exploration of new copper-catalyzed versions of the transformation.The domino transformations are introduced and discussed from five aspects according to the different key processes involved in these reactions.
基金Sichuan Science and Technology Program(No:2020YJ0221)the Natural Science Foundation of Shandong Province,China(No.ZR2021QH362).
文摘Comprehensive Summary Benzothiadiazine-1,1-dioxide scaffold is bioactive framework with wild utility and applications.Synthesis of benzothiadiazine-fused isoquinoline derivatives and spiro benzothiadiazine derivatives through transition metal-catalyzed C—H activation/annulation was reported.3-Phenyl-2H-benzothiadiazine-1,1-dioxide was used as the reaction substrate,and vinylene carbonate and 4-diazopyrazolone were used as the coupling reagents,respectively.This strategy provides straightforward access to complex N-heterocycles in a highly efficient and simple manner.
