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
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
Advances in iron-catalysed cross coupling from 2010-2015 are critically reviewed.In addition to a description of the systems that have emerged since 2010,the significant mechanistic work carried out to understand the ...Advances in iron-catalysed cross coupling from 2010-2015 are critically reviewed.In addition to a description of the systems that have emerged since 2010,the significant mechanistic work carried out to understand the mechanisms of these transformations will be discussed.An emphasis will be placed on mechanistic studies that utilize in situ reaction monitoring and the tools used to achieve this goal.展开更多
Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were...Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.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
A pneumatic parallel platform driven by an air cylinder and three circumambient pneumatic muscles was considered. Firstly, a mathematical model of the pneumatic servo system was developed for the MIMO nonlinear model-...A pneumatic parallel platform driven by an air cylinder and three circumambient pneumatic muscles was considered. Firstly, a mathematical model of the pneumatic servo system was developed for the MIMO nonlinear model-based controller designed. The pneumatic muscles were controlled by three proportional position valves, and the air cylinder was controlled by a proportional pressure valve. As the forward kinematics of this structure had no analytical solution, the control strategy should be designed in joint space. A cross-coupling integral adaptive robust controller(CCIARC) which combined cross-coupling control strategy and traditional adaptive robust control(ARC) theory was developed by back-stepping method to accomplish trajectory tracking control of the parallel platform. The cross-coupling part of the controller stabilized the length error in joint space as well as the synchronization error, and the adaptive robust control part attenuated the adverse effects of modelling error and disturbance. The force character of the pneumatic muscles was difficult to model precisely, so the on-line recursive least square estimation(RLSE) method was employed to modify the model compensation. The projector mapping method was used to condition the RLSE algorithm to bound the parameters estimated. An integral feedback part was added to the traditional robust function to reduce the negative influence of the slow time-varying characteristic of pneumatic muscles and enhance the ability of trajectory tracking. The stability of the controller designed was proved through Laypunov's theory. Various contrast controllers were designed to testify the newly designed components of the CCIARC. Extensive experiments were conducted to illustrate the performance of the controller.展开更多
Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O...Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O,N)usually requires air or moisture‐sensitive and strong reducing agents,which limit the feasibility of substrate scope.Herein we describe a photo‐induced reductive cross‐coupling reaction of aldehydes,ketones and imines with electron‐deficient arenes(aromatic nitriles)using fac‐Ir(ppy)3as a photocatalyst and diisopropylethylamine(DIPEA)as a terminal reductant under visible light irradiation.Mild conditions and high yields mean that this new polarity inversion strategy can be used with aryl‐substituted alcohols and amines.Spectroscopic studies and control experiments have demonstrated the oxidative quenching of Ir(ppy)3*by electron‐deficient arenes involved in the key step for the C–C bond formation.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
Most recent progress on the Suzuki-Miyaura, Heck and Sonogashira cross-coupling reactions, induced by heterobimetallic Pd-Ln coordination polymers as heterogeneous catalysts has been accurately reviewed. Physical-chem...Most recent progress on the Suzuki-Miyaura, Heck and Sonogashira cross-coupling reactions, induced by heterobimetallic Pd-Ln coordination polymers as heterogeneous catalysts has been accurately reviewed. Physical-chemical characterization of the Pd-Ln composite materials by adequate physical methods revealed the distinct structure and configuration of the two- and three-dimensional frameworks. The important contribution of the coordination polymers as catalyst supports to finely modulating the catalytic activity and chemoselectivity has been considered. Published results illustrate the high activity and chemoselectivity of Pd-Ln coordination polymers in cross-coupling reactions, excellent catalyst recoverability and recyclability as well as low catalyst loading or metal leaching, under optimized reaction conditions. The particular effect of the solvent, base, aryl halide or related reagents in governing the main steps of the Pd catalytic cycle has been particularly outlined. In addition, the well-established cooperative effect of the lanthanides with palladium, with emphasis on the synergism between different metals in heterobimetallic catalytic systems, has been highlighted.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
An environmentally friendly method for the synthesis of 3‐organylselenyl quinolones through theelectrochemical cross‐dehydrogenative coupling of 4‐quinolones and diorganyl diselenides wasdeveloped.As a green,atom e...An environmentally friendly method for the synthesis of 3‐organylselenyl quinolones through theelectrochemical cross‐dehydrogenative coupling of 4‐quinolones and diorganyl diselenides wasdeveloped.As a green,atom economic and self‐separating process,the present reaction requiresneither external oxidants nor electrolytes,forming a recyclable catalytic system.展开更多
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
The small size and high electronegativity of the fluorine atom endow it with a remarkable role in organic synthesis,materials science,and medicinal chemistry.The strategic incorporation of fluorine atoms and fluorine-...The small size and high electronegativity of the fluorine atom endow it with a remarkable role in organic synthesis,materials science,and medicinal chemistry.The strategic incorporation of fluorine atoms and fluorine-containing motifs into organic molecules can significantly improve their physicochemical properties,leading to enhanced membrane permeability and superior metabolic stability.展开更多
The hydrolysis of tetramethyldisiloxane,a constituent of silicone industrial refuse,provides a convenient method to generate H_(2)on demand.Herein,highly selective and efficient 2D graphene-like carbon nanosheet(GCN)-...The hydrolysis of tetramethyldisiloxane,a constituent of silicone industrial refuse,provides a convenient method to generate H_(2)on demand.Herein,highly selective and efficient 2D graphene-like carbon nanosheet(GCN)-stabilized Pd,Rh and Ru nanohybrids have been developed as robust catalysts upon hydrolysis of tetramethyldisiloxane for H_(2)generation,Suzuki-Miyaura cross-coupling reactions and 4-nitrophenol reduction.The optimal Pd/GCN nanohybrid shows high catalytic activity in H_(2)generation from tetramethyldisiloxane hydrolysis with a TOF of 375 min^(-1)at 30℃.展开更多
The synthesis and full characterization of several transition metal complexes of a redox-switchable,biaryl(Ar^(T))-substituted[1]phosphaferrocenophane,FcPAr^(T)(L2),in conjunction with some palladium complexes of the ...The synthesis and full characterization of several transition metal complexes of a redox-switchable,biaryl(Ar^(T))-substituted[1]phosphaferrocenophane,FcPAr^(T)(L2),in conjunction with some palladium complexes of the mesityl(Mes)-substituted derivative,FcPMes(L1),and the non-bridged diphenylferrocenyl phosphine,Ph_(2)PFc(L3),are reported.Cyclic voltammetry studies on the bimetallic complexes[Ir(κ^(1)P-L2)(cod)Cl](1),[Ir(κ^(1)P-L2)(CO)2Cl](2),[AuCl(κ^(1)P-L2)](3),[Pd(κ^(1)P-L2)(η^(3)-allyl)Cl](4),[Pd(κ^(1)P-L3)(η^(3)-allyl)Cl](5),[Pd(κ^(1)P-L3)(2-aminobiphenyl)(SO_(3)CH_(3))](6),and[Pd(κ^(1)P-L1)(2-aminobiphenyl)(SO_(3)CH_(3))](7)provided indications for a good electronic communication between the metal atoms.In order to confirm that the[1]ferrocenophane or 1-ferrocenyl unit might be able to electrochemically influence the reactivity of the coordinated transition metal,the palladium complexes 4-7 were employed as redox-switchable catalysts(RSC)in Buchwald-Hartwig cross-coupling reactions.The catalytic activity depends on the ligand and decreases in the series L3>L2>L1.In stirred solutions,the reaction rate can be influenced by addition of an oxidizing reagent.Some reactions were accelerated with in situ generated,cationic complexes as catalysts as compared to their neutral analogs;in some cases,the activity was found to be lower.Furthermore,steric effects play a predominant role,among other factors.展开更多
Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthe...Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.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
We consider a tachyonic model of dark energy in which scalar field non-minimally coupled with curvature and kinetic part of its Lagrangian density.Additionally the model contains the Gauss–Bonnet coupling to the scal...We consider a tachyonic model of dark energy in which scalar field non-minimally coupled with curvature and kinetic part of its Lagrangian density.Additionally the model contains the Gauss–Bonnet coupling to the scalar field through an arbitrary function.The non-minimal Gauss–Bonnet coupling function and scalar field potential have been obtained for power-law solution and then for a dynamically varying equation of state.We have extracted the required condition for the so-called phantom divide line crossing in the model and represented such a crossing numerically.展开更多
In contrast to transition metals,rare-earth metal-promoted sp^(2)-sp carbon-carbon coupling through reductive elimination cannot be realized due to the inaccessibility of two-electron metal-based redox couples.Herein,...In contrast to transition metals,rare-earth metal-promoted sp^(2)-sp carbon-carbon coupling through reductive elimination cannot be realized due to the inaccessibility of two-electron metal-based redox couples.Herein,we report that sp^(2)-sp cross-carbanion coupling has been realized in the reaction of rare-earth azametallacyclopentadienes 2 with alkyl and aryl terminal alkynes.The reaction of 2,which are in situ generated from rare-earth metallacyclopropenes 1 and nitriles,with terminal alkynes provides a new class of seven-membered rare-earth metallacycles 3 containing cumulated double bonds.The structures of complexes 3 have been fully characterized.Mechanistic studies using DFT calculations and principal interacting orbital(PIO)analysis reveal that the formation of 3 proceeds through three steps:activation of the alkynyl C-H bond in terminal alkynes,followed by sp^(2)-sp cross-carbanion coupling and subsequent propargyl-to-allenyl isomerization to form a new C-C double bond,providing metallacycles 3.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 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.
文摘Advances in iron-catalysed cross coupling from 2010-2015 are critically reviewed.In addition to a description of the systems that have emerged since 2010,the significant mechanistic work carried out to understand the mechanisms of these transformations will be discussed.An emphasis will be placed on mechanistic studies that utilize in situ reaction monitoring and the tools used to achieve this goal.
文摘Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.
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Project(51375430)supported by the National Natural Science Foundation of China
文摘A pneumatic parallel platform driven by an air cylinder and three circumambient pneumatic muscles was considered. Firstly, a mathematical model of the pneumatic servo system was developed for the MIMO nonlinear model-based controller designed. The pneumatic muscles were controlled by three proportional position valves, and the air cylinder was controlled by a proportional pressure valve. As the forward kinematics of this structure had no analytical solution, the control strategy should be designed in joint space. A cross-coupling integral adaptive robust controller(CCIARC) which combined cross-coupling control strategy and traditional adaptive robust control(ARC) theory was developed by back-stepping method to accomplish trajectory tracking control of the parallel platform. The cross-coupling part of the controller stabilized the length error in joint space as well as the synchronization error, and the adaptive robust control part attenuated the adverse effects of modelling error and disturbance. The force character of the pneumatic muscles was difficult to model precisely, so the on-line recursive least square estimation(RLSE) method was employed to modify the model compensation. The projector mapping method was used to condition the RLSE algorithm to bound the parameters estimated. An integral feedback part was added to the traditional robust function to reduce the negative influence of the slow time-varying characteristic of pneumatic muscles and enhance the ability of trajectory tracking. The stability of the controller designed was proved through Laypunov's theory. Various contrast controllers were designed to testify the newly designed components of the CCIARC. Extensive experiments were conducted to illustrate the performance of the controller.
文摘Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O,N)usually requires air or moisture‐sensitive and strong reducing agents,which limit the feasibility of substrate scope.Herein we describe a photo‐induced reductive cross‐coupling reaction of aldehydes,ketones and imines with electron‐deficient arenes(aromatic nitriles)using fac‐Ir(ppy)3as a photocatalyst and diisopropylethylamine(DIPEA)as a terminal reductant under visible light irradiation.Mild conditions and high yields mean that this new polarity inversion strategy can be used with aryl‐substituted alcohols and amines.Spectroscopic studies and control experiments have demonstrated the oxidative quenching of Ir(ppy)3*by electron‐deficient arenes involved in the key step for the C–C bond formation.
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 National Key Research and Development Program of China(Grant No.2020YFC1909300).
文摘Most recent progress on the Suzuki-Miyaura, Heck and Sonogashira cross-coupling reactions, induced by heterobimetallic Pd-Ln coordination polymers as heterogeneous catalysts has been accurately reviewed. Physical-chemical characterization of the Pd-Ln composite materials by adequate physical methods revealed the distinct structure and configuration of the two- and three-dimensional frameworks. The important contribution of the coordination polymers as catalyst supports to finely modulating the catalytic activity and chemoselectivity has been considered. Published results illustrate the high activity and chemoselectivity of Pd-Ln coordination polymers in cross-coupling reactions, excellent catalyst recoverability and recyclability as well as low catalyst loading or metal leaching, under optimized reaction conditions. The particular effect of the solvent, base, aryl halide or related reagents in governing the main steps of the Pd catalytic cycle has been particularly outlined. In addition, the well-established cooperative effect of the lanthanides with palladium, with emphasis on the synergism between different metals in heterobimetallic catalytic systems, has been highlighted.
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.
文摘An environmentally friendly method for the synthesis of 3‐organylselenyl quinolones through theelectrochemical cross‐dehydrogenative coupling of 4‐quinolones and diorganyl diselenides wasdeveloped.As a green,atom economic and self‐separating process,the present reaction requiresneither external oxidants nor electrolytes,forming a recyclable catalytic system.
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.
基金financial support from the Scientific Research Fund of Hunan Provincial Education Department(No.22B0435)Changsha Natural Science Foundation(No.104872)。
文摘The small size and high electronegativity of the fluorine atom endow it with a remarkable role in organic synthesis,materials science,and medicinal chemistry.The strategic incorporation of fluorine atoms and fluorine-containing motifs into organic molecules can significantly improve their physicochemical properties,leading to enhanced membrane permeability and superior metabolic stability.
基金support from the National Natural Science Foundation of China(21805166)the 111 Project of China(D20015)+2 种基金the outstanding young and middle-aged science and technology innovation teams,Ministry of Education,Hubei province,China(T2020004)the foundation of Science and Technology Bureau of Yichang City(A21-3-012)China Three Gorges University,the University of Bordeaux and Centre National de la Recherche Scientifique(CNRS)is gratefully acknowledged.
文摘The hydrolysis of tetramethyldisiloxane,a constituent of silicone industrial refuse,provides a convenient method to generate H_(2)on demand.Herein,highly selective and efficient 2D graphene-like carbon nanosheet(GCN)-stabilized Pd,Rh and Ru nanohybrids have been developed as robust catalysts upon hydrolysis of tetramethyldisiloxane for H_(2)generation,Suzuki-Miyaura cross-coupling reactions and 4-nitrophenol reduction.The optimal Pd/GCN nanohybrid shows high catalytic activity in H_(2)generation from tetramethyldisiloxane hydrolysis with a TOF of 375 min^(-1)at 30℃.
基金financial support from the DFG-funded transregional collaborative research centre SFB/TRR 88“Cooperative effects in homo-and heterometallic complexes(3MET)”(project B4).
文摘The synthesis and full characterization of several transition metal complexes of a redox-switchable,biaryl(Ar^(T))-substituted[1]phosphaferrocenophane,FcPAr^(T)(L2),in conjunction with some palladium complexes of the mesityl(Mes)-substituted derivative,FcPMes(L1),and the non-bridged diphenylferrocenyl phosphine,Ph_(2)PFc(L3),are reported.Cyclic voltammetry studies on the bimetallic complexes[Ir(κ^(1)P-L2)(cod)Cl](1),[Ir(κ^(1)P-L2)(CO)2Cl](2),[AuCl(κ^(1)P-L2)](3),[Pd(κ^(1)P-L2)(η^(3)-allyl)Cl](4),[Pd(κ^(1)P-L3)(η^(3)-allyl)Cl](5),[Pd(κ^(1)P-L3)(2-aminobiphenyl)(SO_(3)CH_(3))](6),and[Pd(κ^(1)P-L1)(2-aminobiphenyl)(SO_(3)CH_(3))](7)provided indications for a good electronic communication between the metal atoms.In order to confirm that the[1]ferrocenophane or 1-ferrocenyl unit might be able to electrochemically influence the reactivity of the coordinated transition metal,the palladium complexes 4-7 were employed as redox-switchable catalysts(RSC)in Buchwald-Hartwig cross-coupling reactions.The catalytic activity depends on the ligand and decreases in the series L3>L2>L1.In stirred solutions,the reaction rate can be influenced by addition of an oxidizing reagent.Some reactions were accelerated with in situ generated,cationic complexes as catalysts as compared to their neutral analogs;in some cases,the activity was found to be lower.Furthermore,steric effects play a predominant role,among other factors.
基金funding supports from the National Natural Science Foundation of China(Nos.21732002,22061007,22071036,and 22207022)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules,National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas),the starting grant of Guizhou University[No.(2022)47)]+10 种基金Department of Education,Guizhou Province[Qianjiaohe KY No.(2020)004]The 10 Talent Plan(Shicengci)of Guizhou Province(No.[2016]5649)Science and Technology Department of Guizhou Province(Nos.[Qiankehe-jichu-ZK[2022]zhongdian024],[2018]2802,[2019]1020,QKHJC-ZK[2022]-455)Department of Education of Guizhou Province(No.QJJ(2022)205)Program of Introducing Talents of Discipline to Universities of China(111 Program,No.D20023)at Guizhou UniversitySingapore National Research Foundation under its NRF Investigatorship(No.NRF-NRFI2016–06)Competitive Research Program(No.NRF-CRP22–2019–0002)Ministry of Education,Singapore,under its MOE Ac RF Tier 1 Award(Nos.RG7/20,RG70/21)MOE AcRF Tier 2(No.MOE2019-T2–2–117)MOE AcRF Tier 3 Award(No.MOE2018-T3–1–003)a Chair Professorship Grant,and Nanyang Technological University。
文摘Enones are widely explored in synthetic chemistry as fundamental building blocks for a wide range of reactions and exhibit intriguing biological activities that are pivotal for drug discovery.The development of synthetic strategies for highly efficient preparation of enones thereby receives intense attention,in particular through the transition metal-catalyzed coupling reactions.Here,we describe a carbene-catalyzed cross dehydrogenative coupling(CDC)reaction that enables effective assembly of simple aldehydes and alkenes to afford a diverse set of enone derivatives.Mechanistically,the in situ generated aryl radical is pivotal to“activate”the alkene by forming an allyl radical through intermolecular hydrogen atom transfer(HAT)pathway and thus forging the carbon-carbon bond formation with aldehyde as the acyl synthon.Notably,our method represents the first example on the enone synthesis through coupling of“non-functionalized”aldehydes and alkenes as coupling partners,and offers a distinct organocatalytic pathway to the transition metal-catalyzed coupling transformations.
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.
文摘We consider a tachyonic model of dark energy in which scalar field non-minimally coupled with curvature and kinetic part of its Lagrangian density.Additionally the model contains the Gauss–Bonnet coupling to the scalar field through an arbitrary function.The non-minimal Gauss–Bonnet coupling function and scalar field potential have been obtained for power-law solution and then for a dynamically varying equation of state.We have extracted the required condition for the so-called phantom divide line crossing in the model and represented such a crossing numerically.
基金supported by the National Key R&D Program of China(No.2021YFF0701600)the Natural Science Foundation of China(No.22371006 and 22131001).
文摘In contrast to transition metals,rare-earth metal-promoted sp^(2)-sp carbon-carbon coupling through reductive elimination cannot be realized due to the inaccessibility of two-electron metal-based redox couples.Herein,we report that sp^(2)-sp cross-carbanion coupling has been realized in the reaction of rare-earth azametallacyclopentadienes 2 with alkyl and aryl terminal alkynes.The reaction of 2,which are in situ generated from rare-earth metallacyclopropenes 1 and nitriles,with terminal alkynes provides a new class of seven-membered rare-earth metallacycles 3 containing cumulated double bonds.The structures of complexes 3 have been fully characterized.Mechanistic studies using DFT calculations and principal interacting orbital(PIO)analysis reveal that the formation of 3 proceeds through three steps:activation of the alkynyl C-H bond in terminal alkynes,followed by sp^(2)-sp cross-carbanion coupling and subsequent propargyl-to-allenyl isomerization to form a new C-C double bond,providing metallacycles 3.
