A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl...A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.展开更多
The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to an...The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.展开更多
Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchro...Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchronous driving scheme based on semi-closed-loop cross- coupling integrated feedforward control is proposed. The scheme comprises a position error cross-coupling feedfor-ward control and a load torque identification with feed- forward control. A digital integrated simulation system for the dual servo synchronous drive system is established. Using a 20 t servo broacher, performance analysis of the scheme is conducted based on this simulation system and the simulation results show that systems with traditional parallel or single control have problems when the work- table works with an unbalanced load. However, the system with proposed scheme shows good synchronous perfor- mance and positional accuracy. Broaching tests are performed and the experimental results show that the maximum dual axis synchronization error of the system is only 8μm during acceleration and deceleration processes and the error between the actual running position and the given position is almost zero. A double position servo synchronous driving scheme is presented based on crosscoupled integrated feedforward compensation control, which can improve the synchronization precision.展开更多
Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids und...Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.展开更多
Labyrinth seal can cause steam-exciting, the structural and operating parameters of labyrinth seal have effect on stability of rotor-system. For investigating the coupling influences of the structure and operating par...Labyrinth seal can cause steam-exciting, the structural and operating parameters of labyrinth seal have effect on stability of rotor-system. For investigating the coupling influences of the structure and operating parameters of labyrinth seals on dynamic coefficients, a model of calculating dynamic coefficients of labyrinth seals is presented using a two control volume model. The coupling influences of parameters on cross-coupled stiffness and direct damping of labyrinth seal are discussed. In the conclusion, a reference of preventing steam-exciting vibration and optimum determination of design parameters of labyrinth seals are provided.展开更多
Inverse vulcanized polymers(IVPs) that generated from elemental sulfur and smaller amounts of alkenes have found broad promising applications such as cathode materials for Li-S batteries, dynamic and repairable materi...Inverse vulcanized polymers(IVPs) that generated from elemental sulfur and smaller amounts of alkenes have found broad promising applications such as cathode materials for Li-S batteries, dynamic and repairable materials, optics applications, and metal sorption. However, their exploration in organic synthesis is still unprecedented. Here we first report the application of inverse vulcanized polymers in catalysis for organic transformations. A biomass-derived inverse vulcanized polymer(IVP-EAE) is found to be capable of catalyzing cross-coupling reactions in a transition-metal-free fashion under visible light.This method allows the direct C–H functionalization of pyrroles and N-arylacrylamides with(hetero)aryl halides, respectively, leading to the formation of two sets of structurally important scaffolds including pyrrole-containing biaryls and 3,3-disubstituted oxindoles with high selectivity. We anticipate this study will not only unveil the new potential of IVPs, but also offer a distinct type of catalysts for organic transformations.展开更多
Classical turbulent K closure theory of the atmospheric boundary layer assumes that the vertical turbulent transport flux of any macroscopic quantity is equivalent to that quantity's vertical gradient transport fl...Classical turbulent K closure theory of the atmospheric boundary layer assumes that the vertical turbulent transport flux of any macroscopic quantity is equivalent to that quantity's vertical gradient transport flux. But a cross coupling between the thermodynamic processes and the dynamic processes in the atmospheric system is demonstrated based on the Curier-Prigogine principle of cross coupling of linear thermodynamics. The vertical turbulent transportation of energy and substance in the atmospheric boundary layer is related not only to their macroscopic gradient but also to the convergence and the divergence movement. The transportation of the convergence or divergence movement is important for the atmospheric boundary layer of the heterogeneous underlying surface and the convection boundary layer. Based on this, the turbulent transportation in the atmospheric boundary layer, the energy budget of the heterogeneous underlying surface and the convection boundary layer, and the boundary layer parameterization of land surface processes over the heterogeneous underlying surface are studied. This research offers clues not only for establishing the atmospheric boundary layer theory about the heterogeneous underlying surface, but also for overcoming the difficulties encountered recently in the application of the atmospheric boundary layer theory.展开更多
Ma's CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. Wit...Ma's CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. With this new reaction condition the cross coupling with aryl iodides could be accomplished in 1,4-dioxane instead of DMSO. This reactin also could be carried out in DMF. Furthermore, the coupling yields under the new conditions are usually higher than in Ma's original methods.展开更多
An operationally simple and inexpensive catalyst system was developed for the cross coupling of aryl iodides and bromides with ethyl acetoacetate by using CuI as catalyst and Nmethyl glycine as ligand. The reaction re...An operationally simple and inexpensive catalyst system was developed for the cross coupling of aryl iodides and bromides with ethyl acetoacetate by using CuI as catalyst and Nmethyl glycine as ligand. The reaction represents a novel Cu-catalyzed C-C cross coupling reaction. This procedure is applicable to the preparation of pharmaceutically important α- arylalkanoic acids.展开更多
Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for syn...Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.展开更多
N,N'-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.
The application of the guided missile seeker is to provide stability to the sensor’s line of sight toward a target by isolating it from the missile motion and vibration.The main objective of this paper is not only to...The application of the guided missile seeker is to provide stability to the sensor’s line of sight toward a target by isolating it from the missile motion and vibration.The main objective of this paper is not only to present the physical modeling of two axes gimbal system but also to improve its performance through using fuzzy logic controlling approach.The paper is started by deriving the mathematical model for gimbals motion using Newton’s second law,followed by designing the mechanical parts of model using SOLIDWORKS and converted to xml file to connect dc motors and sensors using MATLAB/SimMechanics.Then,a Mamdani-type fuzzy and a Proportional-Integral-Derivative(PID)controllers were designed using MATLAB software.The performance of both controllers was evaluated and tested for different types of input shapes.The simulation results showed that self-tuning fuzzy controller provides better performance,since no overshoot,small steady-state error and small settling time compared to PID controller.展开更多
The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol%Cu(OAc)_(2)·H_(2)O and 15 mol%2,2'-biimidazole works at 80℃in DMSO for 3 h to provide a ...The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol%Cu(OAc)_(2)·H_(2)O and 15 mol%2,2'-biimidazole works at 80℃in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields.展开更多
Eight N heterocyclic carbenes (NHC), generated in situ from their imidazolium salts, as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononitrile anion. It was foun...Eight N heterocyclic carbenes (NHC), generated in situ from their imidazolium salts, as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononitrile anion. It was found that 1,3 bis(2,4,6 trimethylphenyl) imidazolium chloride (IMesHCl) Pd 2(dba) 3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts. The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give cross coupling products in yields from 50% to 96%.展开更多
A novel domino cross dehydrogenative coupling of 2-aryl acetals with unmodified ketones has been developed, using DDQ as both the oxidant and reactant precursor.
A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted indenoindole...A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted indenoindole and the mechanism of this reaction was discussed.展开更多
Computational investigations of Cu(I)-catalyzed C--N coupling between aryl halides and aqueous ammonia without addition of any base or ligand were reported. Density functional theory calculations were performed to r...Computational investigations of Cu(I)-catalyzed C--N coupling between aryl halides and aqueous ammonia without addition of any base or ligand were reported. Density functional theory calculations were performed to re- veal the mechanism of the ligand-free amination reaction for the preparation of primary aromatic amines. Through systematic evaluation of the relative concentrations of possible Cu species in solution, we propose that the active catalyst is the neutral Cu(I) complexes rather than the Cu(I) cations; oxidative addition of aryl bromide is a facile step of the catalytic cycle; reactant (NH3) and solvent molecule (NMP) can act as ligands of Cu species to help re- duce the activation energy of the forward reaction and increase the activation energy of the reverse reaction; except for Pathway B, the deprotonation step is irreversible due to the extreme exothermic feature; the elimination of H20 is kinetically favored, while that of HBr is thermodynamically preferred. These findings should be valuable for the mechanism understandings of the ligand-free Cu-catalyzed C--N cross-coupling reactions and for the further de- velopment of highly efficient amination catalyst systems.展开更多
An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been success- fully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective...An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been success- fully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective and operationally convenient process for the synthesis of biaryls, stilbenes and acrylates. Wide scope of substrates, good to excellent yields, low reaction time, water as solvent, ligand-free, non-toxicity and recyclability of the catalyst are the main merits of these protocols. In addition, the h-BN@y-CD@Pd(II) nanomaterial has been fully characte- rized by TG, SEM, IR, XRD, XPS and ICP-AES analysis. And it could be easily recovered and reused for at least nine times without any considerable loss of catalytic activity. Above all, this work demonstrates the possibility of using cyclodextrin-modified h-BN as an efficient support for the hydrophilic heterogeneous catalysts.展开更多
Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctiona...Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctionalized 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylper- oxide gave above intermediates in high yields. The mild reaction conditions and easy purification procedures of this method provide a new approach for the synthesis of phenanthrenes.展开更多
基金the National Natural Science Foundation of China(No.22271245)the Jiangxi Province Science and Technology Project(Nos.20212AEI91002 and 20202ACBL213002)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2021ZD01)for financial support.
文摘A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpolung C–S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functionality tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules.Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni^(0)/Ni^(Ⅰ)/Ni^(Ⅲ)/Ni^(I) catalytic cycle.
基金the Basic Science Research Program(No.NRF-2019R1A2C4069764)by Convergent Technology R&D Program for Hum an Augm entation(No.2019M3C1B8077549)through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT.
文摘The challenge for single-atom catalysts in various C-C cross coupling reaction exists in the development of solid supporting materials.It has been desired tofind a supporting material designed in molecular level to anchor a single-atom catalyst and provide high degree of dispersion and substrate access in aqueous media.Here,we prepared discrete cages of metal-organic polyhedra anchoring single Pd atom(MOP-BPY(Pd))and successfully performed a Suzuki-Miyaura cross coupling reaction with various substrates in aqueous media.It was revealed that each tetrahedral cage of MOP-BPY(Pd)has 4.5 Pd atoms on average and retained its high degree of dispersion up to 3 months in water.The coupling efficiencies of the Suzuki-Miyaura cross coupling reaction exhibited more than 90.0%for various substrates we have tested in the aqueous media,which is superior to those of the molecular Pd complex and metal-organic framework(MOF)anchoring Pd atoms.Moreover,MOP-BPY(Pd)was successfully recovered and recycled without performance degradation.
基金Supported by National Natural Science Foundation of China(Grant No.51307151)Zhejiang Provincial Public Welfare Technology Application Research Project of China(Grant No.2015C31078)+2 种基金Zhejiang Provincial Natural Science Foundation of China(Grant No.LY14E070008)Zhejiang Postdoctoral Science Foundation of China(Grant No.BSH1402065)Science Foundation of Zhejiang SciTech University(Grant No.13022151-Y)
文摘Synchronization errors directly deteriorate the machining accuracy of metal parts and the existed method cannot keep high synchronization precision because of external disturbances. A new double position servo synchronous driving scheme based on semi-closed-loop cross- coupling integrated feedforward control is proposed. The scheme comprises a position error cross-coupling feedfor-ward control and a load torque identification with feed- forward control. A digital integrated simulation system for the dual servo synchronous drive system is established. Using a 20 t servo broacher, performance analysis of the scheme is conducted based on this simulation system and the simulation results show that systems with traditional parallel or single control have problems when the work- table works with an unbalanced load. However, the system with proposed scheme shows good synchronous perfor- mance and positional accuracy. Broaching tests are performed and the experimental results show that the maximum dual axis synchronization error of the system is only 8μm during acceleration and deceleration processes and the error between the actual running position and the given position is almost zero. A double position servo synchronous driving scheme is presented based on crosscoupled integrated feedforward compensation control, which can improve the synchronization precision.
基金the National Natural Science Foundation of China (Nos. 21572036, 21172045 and 91127041)the Changjiang Scholars and Innovative Research Team in University (No. IRT-15R12)+2 种基金the Shanghai International Cooperation Program (No. 14230710600)the Doctoral Fund of Ministry of Education of China (No. 20130071110032)Department of Chemistry Fudan University
文摘Pyridine-bridged bis-benzimidazolylidene nickel complexes exhibited very high catalytic activity toward cross coupling of inactive(hetero)aryl benzylic ammonium salts with(hetero)aryl and alkenyl boronic acids under mild reaction conditions.Even at 2 mol% catalyst loading,a wide range of substrates for both coupling partners with different steric and electronic properties were well tolerated.
基金This project is supported by National Natural Science Foundation of China(59990472). Manuscript received on November 30, 1999 r
文摘Labyrinth seal can cause steam-exciting, the structural and operating parameters of labyrinth seal have effect on stability of rotor-system. For investigating the coupling influences of the structure and operating parameters of labyrinth seals on dynamic coefficients, a model of calculating dynamic coefficients of labyrinth seals is presented using a two control volume model. The coupling influences of parameters on cross-coupled stiffness and direct damping of labyrinth seal are discussed. In the conclusion, a reference of preventing steam-exciting vibration and optimum determination of design parameters of labyrinth seals are provided.
基金the National Natural Science Foundation of China (NSFC, Nos. 22071024, 22271047)the Natural Science Foundation of Fujian Province (Nos.2021J06020, 2022J011121)the Top-Notch Young Talents Program of China, and the Science and Technology Project of Minjiang University (No.MJY21027) for generous financial support。
文摘Inverse vulcanized polymers(IVPs) that generated from elemental sulfur and smaller amounts of alkenes have found broad promising applications such as cathode materials for Li-S batteries, dynamic and repairable materials, optics applications, and metal sorption. However, their exploration in organic synthesis is still unprecedented. Here we first report the application of inverse vulcanized polymers in catalysis for organic transformations. A biomass-derived inverse vulcanized polymer(IVP-EAE) is found to be capable of catalyzing cross-coupling reactions in a transition-metal-free fashion under visible light.This method allows the direct C–H functionalization of pyrroles and N-arylacrylamides with(hetero)aryl halides, respectively, leading to the formation of two sets of structurally important scaffolds including pyrrole-containing biaryls and 3,3-disubstituted oxindoles with high selectivity. We anticipate this study will not only unveil the new potential of IVPs, but also offer a distinct type of catalysts for organic transformations.
基金supported by the National Natural Science Foundation of China under Grant Nos.49835010 and 40233035
文摘Classical turbulent K closure theory of the atmospheric boundary layer assumes that the vertical turbulent transport flux of any macroscopic quantity is equivalent to that quantity's vertical gradient transport flux. But a cross coupling between the thermodynamic processes and the dynamic processes in the atmospheric system is demonstrated based on the Curier-Prigogine principle of cross coupling of linear thermodynamics. The vertical turbulent transportation of energy and substance in the atmospheric boundary layer is related not only to their macroscopic gradient but also to the convergence and the divergence movement. The transportation of the convergence or divergence movement is important for the atmospheric boundary layer of the heterogeneous underlying surface and the convection boundary layer. Based on this, the turbulent transportation in the atmospheric boundary layer, the energy budget of the heterogeneous underlying surface and the convection boundary layer, and the boundary layer parameterization of land surface processes over the heterogeneous underlying surface are studied. This research offers clues not only for establishing the atmospheric boundary layer theory about the heterogeneous underlying surface, but also for overcoming the difficulties encountered recently in the application of the atmospheric boundary layer theory.
文摘Ma's CuI/proline procedure for the catalytic cross coupling between nitrogen heterocycles and aryl halides was markedly improved. The key finding was that K3PO4 was a much better base than K2CO3 for the reaction. With this new reaction condition the cross coupling with aryl iodides could be accomplished in 1,4-dioxane instead of DMSO. This reactin also could be carried out in DMF. Furthermore, the coupling yields under the new conditions are usually higher than in Ma's original methods.
文摘An operationally simple and inexpensive catalyst system was developed for the cross coupling of aryl iodides and bromides with ethyl acetoacetate by using CuI as catalyst and Nmethyl glycine as ligand. The reaction represents a novel Cu-catalyzed C-C cross coupling reaction. This procedure is applicable to the preparation of pharmaceutically important α- arylalkanoic acids.
文摘Cu-catalyzed cross coupling between phosphinic amides and aryl halides was accomplished for the first time by using (±)-trans-cyclohexane-1,2-diamine as the ligand. This reaction provided a novel approach for synthesizing arylated phosphinic amides. Both kinetic measurement and theoretical calculation indicated that phosphinic amides were much less reactive than amides by about 10 times in Cu-catalyzed cross coupling.
文摘N,N'-Diarylhydrazines have been prepared via the reaction of N-Boc-aryl hydrazines with boronic acids mediated by copper acetate. This mild reaction condition tolerates the presence of a variety of functional groups.
基金Taif University Researchers Supporting Project number(TURSP-2020/260),Taif University,Taif,Saudi Arabia.
文摘The application of the guided missile seeker is to provide stability to the sensor’s line of sight toward a target by isolating it from the missile motion and vibration.The main objective of this paper is not only to present the physical modeling of two axes gimbal system but also to improve its performance through using fuzzy logic controlling approach.The paper is started by deriving the mathematical model for gimbals motion using Newton’s second law,followed by designing the mechanical parts of model using SOLIDWORKS and converted to xml file to connect dc motors and sensors using MATLAB/SimMechanics.Then,a Mamdani-type fuzzy and a Proportional-Integral-Derivative(PID)controllers were designed using MATLAB software.The performance of both controllers was evaluated and tested for different types of input shapes.The simulation results showed that self-tuning fuzzy controller provides better performance,since no overshoot,small steady-state error and small settling time compared to PID controller.
基金This work was supported by the Team Innovation Project of Soochow University.
文摘The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol%Cu(OAc)_(2)·H_(2)O and 15 mol%2,2'-biimidazole works at 80℃in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields.
文摘Eight N heterocyclic carbenes (NHC), generated in situ from their imidazolium salts, as ligands of palladium complexes were used for the catalytic coupling of iodobenzene with malononitrile anion. It was found that 1,3 bis(2,4,6 trimethylphenyl) imidazolium chloride (IMesHCl) Pd 2(dba) 3 catalytic system has the highest activity to obtain phenyl malononitrile among the imidazolium salts. The substituted iodoarenes reacted with malononitrile anions by using the catalytic system to give cross coupling products in yields from 50% to 96%.
文摘A novel domino cross dehydrogenative coupling of 2-aryl acetals with unmodified ketones has been developed, using DDQ as both the oxidant and reactant precursor.
文摘A nickel-based catalyst was employed for the first time in the crossing-coupling of indenoindoles with bromo-/iodoarenes. A simple and practical method was provided for the synthesis of N-aryl substituted indenoindole and the mechanism of this reaction was discussed.
文摘Computational investigations of Cu(I)-catalyzed C--N coupling between aryl halides and aqueous ammonia without addition of any base or ligand were reported. Density functional theory calculations were performed to re- veal the mechanism of the ligand-free amination reaction for the preparation of primary aromatic amines. Through systematic evaluation of the relative concentrations of possible Cu species in solution, we propose that the active catalyst is the neutral Cu(I) complexes rather than the Cu(I) cations; oxidative addition of aryl bromide is a facile step of the catalytic cycle; reactant (NH3) and solvent molecule (NMP) can act as ligands of Cu species to help re- duce the activation energy of the forward reaction and increase the activation energy of the reverse reaction; except for Pathway B, the deprotonation step is irreversible due to the extreme exothermic feature; the elimination of H20 is kinetically favored, while that of HBr is thermodynamically preferred. These findings should be valuable for the mechanism understandings of the ligand-free Cu-catalyzed C--N cross-coupling reactions and for the further de- velopment of highly efficient amination catalyst systems.
基金Supported by the National Natural Science Foundation of China(Nos.81373259, 81573286).
文摘An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been success- fully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective and operationally convenient process for the synthesis of biaryls, stilbenes and acrylates. Wide scope of substrates, good to excellent yields, low reaction time, water as solvent, ligand-free, non-toxicity and recyclability of the catalyst are the main merits of these protocols. In addition, the h-BN@y-CD@Pd(II) nanomaterial has been fully characte- rized by TG, SEM, IR, XRD, XPS and ICP-AES analysis. And it could be easily recovered and reused for at least nine times without any considerable loss of catalytic activity. Above all, this work demonstrates the possibility of using cyclodextrin-modified h-BN as an efficient support for the hydrophilic heterogeneous catalysts.
基金Sichuan Provincial Education Department(No.12ZA141)Key Laboratory of Advanced Functional Materials of Sichuan Province Higher Education System (No.KFKT2013-01)Sichuan Normal University(No.XYZ201314-37)for financial support
文摘Polymethoxy-substituted phenanthrene-9-carboxylic acids or their methylate are key intermediates for the synthesis of tylophora alkaloids and their analogs. An intramolecular oxidative coupling reaction of unfunctionalized 2,3-disubstituted phenyl acrylic acids and derivatives promoted by di-tert-butylper- oxide gave above intermediates in high yields. The mild reaction conditions and easy purification procedures of this method provide a new approach for the synthesis of phenanthrenes.