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
Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capa...Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.展开更多
A simple Cu（OAc）2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired ...A simple Cu（OAc）2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu（OAc）2 as the catalyst and Et3N as the solvent.展开更多
The present paper deals with the polymerization of ( R ) 3,3′ diiodo 2,2′ binaphtho 20 crown 6 with \{ p divinylbenzene\} under Heck coupling reaction condition. Both the monomers and the polymer were analyzed by NM...The present paper deals with the polymerization of ( R ) 3,3′ diiodo 2,2′ binaphtho 20 crown 6 with \{ p divinylbenzene\} under Heck coupling reaction condition. Both the monomers and the polymer were analyzed by NMR, FTIR, UV, CD, fluorescent spectroscopy, polarimetry, GPC and elemental analysis. The polymer can emit a strong blue fluorescence and is expected to have the potential application in the polarized blue light emitting sensors. The chiral conjugated polymer exhibits a strong Cotton effect in its Circular Dichroism(CD ) spectrum, indicating the high rigidity of the polymer backbone.展开更多
Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phen...Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.展开更多
The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT （density functional theory） calculations. The model system studied consists of Pd（PH3）2 as the startin...The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT （density functional theory） calculations. The model system studied consists of Pd（PH3）2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages： oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium（Ⅱ） intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium（Ⅱ） diphosphine intermediate. Starting from the palladium（Ⅱ） diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium（Ⅱ） intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.展开更多
A mild, cascade type methodology was developed for the synthesis of polyphenolic ethers by the palladium-catalyzed cross coupling of phenols and halo compounds under microwave heating. In most cases, reactions run in ...A mild, cascade type methodology was developed for the synthesis of polyphenolic ethers by the palladium-catalyzed cross coupling of phenols and halo compounds under microwave heating. In most cases, reactions run in neat conditions and in some cases, IPA/water mixture, and 1,4-dioxane were employed as solvents to furnish the products. By applying this new method, we were able to synthesize and purify a good number of polyether compounds with complete spectral data.展开更多
We present a systematic study of 6Li elastic scattering and total reaction cross sections at incident energies around the Coulomb barrier within the continuum discretized coupled-channels(CDCC)framework,where 6Li is t...We present a systematic study of 6Li elastic scattering and total reaction cross sections at incident energies around the Coulomb barrier within the continuum discretized coupled-channels(CDCC)framework,where 6Li is treated in anα+d two-body model.Collisions with 27Al,64Zn,138Ba,and 208Pa are analyzed.The microscopic optical potentials(MOP)based on Skyrme nucleon-nucleon interaction forαand d are adopted in CDCC calculations and satisfactory agreement with the experimental data is obtained without any adjustment on MOPs.For comparison,αand d global phenomenological optical potentials(GOP)are also used in CDCC analysis and a reduction of no less than 50%on the surface imaginary part of deuteron GOP is required for describing the data.In all cases,the 6Li breakup effect is significant and provides repulsive correction to the folding model potential.The reduction on the surface imaginary part of GOP of deuteron reveals a strong suppression of the reaction probability of deuteron as a component of 6Li when compared with that of a free deuteron.Further investigation is performed by considering the d breakup process equivalently within the dynamic polarization potential approach,and the results show that d behaves in a manner similar to a tightly bound nucleus in 6Li induced reactions.展开更多
A simple arylhydrazone containing the benzothiazole moiety which may be used as an efficient ligand in the palladium-catalyzed Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions, under infrared irradiation as a...A simple arylhydrazone containing the benzothiazole moiety which may be used as an efficient ligand in the palladium-catalyzed Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions, under infrared irradiation as an alternative source of energy, is presented. The reactions proceeded with extremely high efficiency under mild conditions and produced very good yields.展开更多
大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂...大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂量)能够在甲苯中有效地催化溴代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应,产率在32%～99%之间,TON值可达到6×104,同时反应过程中没有钯黑析出。展开更多
Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and （Z）-4-aryl-but-2- en-l-ols were found to have choleretic activity. Strategies have been reported to synthesize （E）-4-a...Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and （Z）-4-aryl-but-2- en-l-ols were found to have choleretic activity. Strategies have been reported to synthesize （E）-4-aryl-but-2-en-l- ols with high selectivity. However, there is no method to obtain （Z）-4-aryl-but-2-en-1-ols with high selectivity now. We developed a Suzuki-Miyaura cross-coupling reaction of 1,2-oxaborol-2（5H）-ols with benzyl bromides to synthesize （Z）-4-aryl-but-2-en-1-ols, the products were obtained in up to 94% isolated yield.展开更多
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 the National Natural Science Foundation of China(21176038,21576044,21536002)the Science Fund for Creative Research Groups of the National Natural Science Foundation of China(21421005)the Dalian University of Technology Innovation Team(DUT2013TB07)
文摘Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.
文摘A simple Cu（OAc）2 catalyzed Sonogashira coupling protocol is presented. It was found that the couplings of a variety of aryl halides with terminal alkynes were conducted smoothly to afford the corresponding desired products in moderate to excellent yields, using Cu（OAc）2 as the catalyst and Et3N as the solvent.
文摘The present paper deals with the polymerization of ( R ) 3,3′ diiodo 2,2′ binaphtho 20 crown 6 with \{ p divinylbenzene\} under Heck coupling reaction condition. Both the monomers and the polymer were analyzed by NMR, FTIR, UV, CD, fluorescent spectroscopy, polarimetry, GPC and elemental analysis. The polymer can emit a strong blue fluorescence and is expected to have the potential application in the polarized blue light emitting sensors. The chiral conjugated polymer exhibits a strong Cotton effect in its Circular Dichroism(CD ) spectrum, indicating the high rigidity of the polymer backbone.
基金supported by the National Natural Science of Foundation of China(21676140)the fund from the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201402)the Project of Priority Academic Program Development(PAPD) of Jiangsu Higher Education Institutions~~
文摘Palladium nanoparticles supported on cross-linked polyaniline with bulky phosphorus ligands were developed.These catalysts showed high efficiency in the Suzuki-Miyaura reaction of aryl chlorides and bromides with phenylboronic acids.Aryl chlorides and bromides with functional groups,such as CN,MeO,CHO,MeCO and NO_2,were converted to the corresponding biphenyls in high yields with catalyst loading.Additionally,the catalysts combined high activity with good reusability;they could be used at least five times for the Suzuki-Miyaura coupling reaction.
基金Supported by the NNSFC (No. 20464001 and 20674034)
文摘The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT （density functional theory） calculations. The model system studied consists of Pd（PH3）2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages： oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium（Ⅱ） intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium（Ⅱ） diphosphine intermediate. Starting from the palladium（Ⅱ） diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium（Ⅱ） intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.
文摘A mild, cascade type methodology was developed for the synthesis of polyphenolic ethers by the palladium-catalyzed cross coupling of phenols and halo compounds under microwave heating. In most cases, reactions run in neat conditions and in some cases, IPA/water mixture, and 1,4-dioxane were employed as solvents to furnish the products. By applying this new method, we were able to synthesize and purify a good number of polyether compounds with complete spectral data.
基金Supported by the National Natural Science Foundation of China(U2067205)。
文摘We present a systematic study of 6Li elastic scattering and total reaction cross sections at incident energies around the Coulomb barrier within the continuum discretized coupled-channels(CDCC)framework,where 6Li is treated in anα+d two-body model.Collisions with 27Al,64Zn,138Ba,and 208Pa are analyzed.The microscopic optical potentials(MOP)based on Skyrme nucleon-nucleon interaction forαand d are adopted in CDCC calculations and satisfactory agreement with the experimental data is obtained without any adjustment on MOPs.For comparison,αand d global phenomenological optical potentials(GOP)are also used in CDCC analysis and a reduction of no less than 50%on the surface imaginary part of deuteron GOP is required for describing the data.In all cases,the 6Li breakup effect is significant and provides repulsive correction to the folding model potential.The reduction on the surface imaginary part of GOP of deuteron reveals a strong suppression of the reaction probability of deuteron as a component of 6Li when compared with that of a free deuteron.Further investigation is performed by considering the d breakup process equivalently within the dynamic polarization potential approach,and the results show that d behaves in a manner similar to a tightly bound nucleus in 6Li induced reactions.
文摘A simple arylhydrazone containing the benzothiazole moiety which may be used as an efficient ligand in the palladium-catalyzed Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions, under infrared irradiation as an alternative source of energy, is presented. The reactions proceeded with extremely high efficiency under mild conditions and produced very good yields.
文摘大力发展非磷配体的钯催化C-C偶联具有重要的理论意义和应用价值。本文设计合成了3个结构稳定、毒性小的卟啉钯配合物,并利用1 H NMR和IR对其结构进行了表征。3个配合物的催化活性结果表明:四(甲氧基苯基)卟啉钯(配合物3,0.1%mol催化剂量)能够在甲苯中有效地催化溴代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应,产率在32%～99%之间,TON值可达到6×104,同时反应过程中没有钯黑析出。
基金support from National Natural Science Foundation of China （Nos. 20802088, 91017006, 90917017） and the Fundamental Research Funds for the Central Universities.
文摘Z and E configuration 4-aryl-but-2-en-1-ols were isolated from several terrestrial plants, and （Z）-4-aryl-but-2- en-l-ols were found to have choleretic activity. Strategies have been reported to synthesize （E）-4-aryl-but-2-en-l- ols with high selectivity. However, there is no method to obtain （Z）-4-aryl-but-2-en-1-ols with high selectivity now. We developed a Suzuki-Miyaura cross-coupling reaction of 1,2-oxaborol-2（5H）-ols with benzyl bromides to synthesize （Z）-4-aryl-but-2-en-1-ols, the products were obtained in up to 94% isolated yield.
