Acrylonitrile reacts with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound arsine palladium(0) complex to afford stereoselectively (E)-cinnamo- nitriles in high yields.
Arylation of acrylamide and acrylonitrile were carried out with various arenediazonium tetrafluoroborates in the presence of a catalytic amount of Pd(OAc)(2) in ethanol and a variety of substituted (E)-cinnamamides an...Arylation of acrylamide and acrylonitrile were carried out with various arenediazonium tetrafluoroborates in the presence of a catalytic amount of Pd(OAc)(2) in ethanol and a variety of substituted (E)-cinnamamides and (E)-cinnamonitriles were obtained in high yields under mild reaction conditions.展开更多
Allyl and cinnamyl and propargyl bromide reacted under mild conditions with triarylbismuth under catalysis by Pd(O) to give 3-arylpropenes, 1, 3-diarylpropenes and arylpropadienes in modest to excellent yields.
(?)-Aryl-(?)-cyanosulfones are prepared under mild conditions with good yields by using palladium-catalyzed coupling reaction between aryl halides and (?)-cyanosulfones in the presence of phase transfer catalyst.
α-C(sp^(3))-H arylation is an important type of C-H functionalization.Various biologically significant natural products,chemi-cal intermediates,and drugs have been effectively prepared via C-H functionalization.Cycli...α-C(sp^(3))-H arylation is an important type of C-H functionalization.Various biologically significant natural products,chemi-cal intermediates,and drugs have been effectively prepared via C-H functionalization.Cyclic carbonyl compounds comprise of cyclic ketones,enones,lactones,and lactams.Theα-C(sp^(3))-H arylation of these compounds have been exhibited high efficiency in forming C(sp^(3))-C(sp^(2))bonds,played a crucial role in organic synthesis,and attracted majority of interests from organic and medicinal communities.This review focused on the most significant advances including methods,mechanism,and applications in total synthesis of natural products in the field ofα-C(sp^(3))-H arylations of cyclic carbonyl compounds in recent years.展开更多
Allylic alcohols react with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound bidentate sulfur palladium (0) complex to form 3-arylaldehydes or ketones in good yields.
The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction...The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.展开更多
The rapid synthesis of structurally complicated electron donors&acceptors still remains a major challenge in organic solar cells(OSC).In this work,we developed a highly efficient strategy to access long-chain olig...The rapid synthesis of structurally complicated electron donors&acceptors still remains a major challenge in organic solar cells(OSC).In this work,we developed a highly efficient strategy to access long-chain oligomeric donor and acceptors for OSC applications.A series of cyclopentadithiophene(CPDT)and benzothiadiazole(BT)-basedπ-conjugated oligomers,i.e.,three oligomeric acceptors(BTDT)n-IC(n=1—3)and one long-chain oligomeric donor(BTDT)4-RD,are facilely synthesized by an atom-and step-economical,and labor-saving direct C—H arylation(DACH)reaction(i.e.,C—H/C—Br cross coupling).Note that(BTDT)4-RD involving five CPDT,four BT and two rhodamine(RD)building blocks is the longest oligomeric donor in the fullerene-free OSC devices ever reported.The dependence of the structure-property-performance correlation of(BTDT)n-IC(n=1—3)and(BTDT)4-RD on theπ-conjugation lengths is thoroughly investigated by opto-electrochemical measurements,bulk heterojunction(BHJ)OSC devices and microscopies.The(BTDT)1-IC:PBDB-T and(BTDT)4-RD:Y6 BHJs achieve power conversion efficiencies of 9.14%and 4.51%,respectively.Our findings demonstrate that DACH reaction is a powerful tool to tune the opto-electronic properties and device performances by regulating the lengths ofπ-conjugated oligomers with varied numbers of repeating units.展开更多
We report the unprecedent Pd(I)catalyzed ring-opening arylation of cyclopropyl-α-aminoamides.This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challengin...We report the unprecedent Pd(I)catalyzed ring-opening arylation of cyclopropyl-α-aminoamides.This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challenging peptide-natural product conjugates.Site selectivity was achieved by introduction of special unnatural amino acids,which also meets the requisite of bioorthogonal chemistry.Mechanism investigations reveals a distinct domino radical ring-opening process through Pd(I)catalysis.展开更多
Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β...Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β-aryl esters has been disclosed,using the native amino as the directing group.A variety of chiralα-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono-and di-arylated products.展开更多
Direct arylation polycondensation(DArP)has emerged as an eco-friendly and atom-efficient methodology for the syntheses ofπ-conjugated polymers(CPs).This approach features the direct C—H arylation of an aromatic hydr...Direct arylation polycondensation(DArP)has emerged as an eco-friendly and atom-efficient methodology for the syntheses ofπ-conjugated polymers(CPs).This approach features the direct C—H arylation of an aromatic hydrocarbon with an aryl halide.Given the prevalence of thiophene-containing CPs,achieving efficient and defect-free DArP of thiophene-based C−H monomers is of great significance.This review presents a mechanistic insight into DArP and describes the development of DArP catalytic systems for varied thiophene-based C−H monomers.Moreover,the control of the primary defects(i.e.,branching and homo-coupling)in thiophene-based DArP is also elaborated.By emphasizing the principles behind monomer selection and catalytic system optimization,this review intends to provide a framework for future advancements in the DArP of thiophene-containing CPs.展开更多
The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorot...The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorothien-2-yl)ethene)(PFuD PP-4FTVT),in variou s organic solvents was studied.The polymer is soluble in 3-methylcyclohexanone(3-MC),a green solvent from peppermint oil,besides other solvents such as anisole,cyclopentyl methyl ether(CPME)and o-dichlorobenzene(o-DCB),etc.Based on the Hansen solu bility parameters(HSP)analysis,3-MC is identified as a"marginal solvent"of PFuDPP-4FTVT.The morphology of the spin-coated films with 3-MC as the solvent strongly correlated with the solution preparation conditions.With a 3-MC solution aged for 3 h at 70℃,n-channel organic thin-film transistors(OTFTs)with electron mobility(μe)above 1 cm^(2)·V^(-1)·s^(-1) and current on/off ratio(Ion/Ioff)higher than 105 were fabricated by spin-coating.This is the first report on high mobility conjugated polymers for OTFTs processible with natu rally occurred green solvent.展开更多
As the high calibre candidate of lightweight and flexible solar cells,polymer solar cells(PSCs)have made tremendous progress in recent years.However,the active photovoltaic materials in PSCs are mainly synthesized by ...As the high calibre candidate of lightweight and flexible solar cells,polymer solar cells(PSCs)have made tremendous progress in recent years.However,the active photovoltaic materials in PSCs are mainly synthesized by metal-mediated coupling reaction requiring harsh reaction conditions,multiple-step synthesis,and cumbersome purification,which is not cost-efficient and may bring toxicity concerns.It is not favorable to the production of photovoltaic polymers and PSC devices on a large scale,and therefore unsuitable for the PSCs industrialization.Direct arylation coupling reaction via aromatic C―H bonds activation enables the synthesis of conjugated polymers under mild conditions and simultaneously reduces synthetic steps,difficulty,and toxic reaction byproducts.This review provides an overview of the history of preparing representative photovoltaic polymers utilized in PSCs through direct arylation reactions and discusses the activity and selectivity of C―H bonds in typical building blocks under different reaction conditions.Especially,the impact of direct arylation condition on defect formation and photovoltaic performance of the photovoltaic polymers is addressed and compared with conventional Stille coupling methods.展开更多
A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensatio...A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensation (DArP) is presented. Through detailed study, we found that the inhibitory effect of 7,7'-diazaisoindigo on DArP stemmed from the coordination of N atom with catalyst can be overcome by using dimethylacetamide (DMAc) as the co-solvent. Thus, PAIID-4FTVT with number-average molecular weight (Mn)>100kDa was synthesized via DArP by optimizing the content of DMAc. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy revealed that PAIID-4FTVT was defect-free. Top gate and bottom contact (TG/BC) organic thin-film transistors (OTFTs) were fabricated to characterize the semiconducting properties of the polymers. PAIID-4FTVT displayed unipolar n-type characteristics with the electron mobility (μe) strongly dependent on Mn. The highest μe up to 0.25 cm^2·V^-1 s^-1 was achieved with the high molecular weight sample.展开更多
A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with sec...A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.展开更多
10 mol% Cul combined with the DMEDA ligand can efficiently catalyze the N-arylation of 2-arylindoles with aryl iodides and aryl bromides in good to excellent yields. The aryl halides bearing electron-rich or electron-...10 mol% Cul combined with the DMEDA ligand can efficiently catalyze the N-arylation of 2-arylindoles with aryl iodides and aryl bromides in good to excellent yields. The aryl halides bearing electron-rich or electron-deficient functional groups can be well tolerated under this mild reaction conditions.展开更多
PAD4 is a promising epigenetic drug target for various cancers and immune diseases. In this work, we applied a Cu-catalyzed C–H arylation reaction of N-heteroarene to the synthesis of complex non-covalent PAD4 inhibi...PAD4 is a promising epigenetic drug target for various cancers and immune diseases. In this work, we applied a Cu-catalyzed C–H arylation reaction of N-heteroarene to the synthesis of complex non-covalent PAD4 inhibitors bearing a bi-heteroaryl pharmacophore. This strategy allowed us to access various analogs of C_2-aryl substituted benzimidazoles from a common benzimidazole core and easily accessible aryl iodides. Preliminary SAR studies revealed the indole motif of GSK-484 is critical to its activity. Replacing the N-cyclopropylmethyl group to N-benzyl group on the indole ring of GSK-484 resulted in more than5-fold increase in cell killing efficacy against 4T1 cell line.展开更多
We report a practical and highly efficient protocol for the arylation of pyridine N-oxides with arylboronic acid through palladium-catalyzed Suzuki reaction in water.This ligand-free Suzuki reaction is performed in th...We report a practical and highly efficient protocol for the arylation of pyridine N-oxides with arylboronic acid through palladium-catalyzed Suzuki reaction in water.This ligand-free Suzuki reaction is performed in the presence of diisopropylamine and gives 2-or 3-arylated pyridyl N-oxide derivatives in good to excellent yields within 1 h.展开更多
Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs)and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT)for new donor-acceptor conjugated polymer...Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs)and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT)for new donor-acceptor conjugated polymers.The polymers exhibited blue hues in neutralstate with distinct color-to-transmissive reversible electrochromic switching under applied potentials from 0 V to+1.5 V,and showed high coloration efficiencies(436-438 cm^(2)·C^(-1))in near-infrared regions with high switching speeds around 1-2 s under ambient conditions.展开更多
Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading (5 mol% of Cul). A variety of aryl iodides could he aminated...Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading (5 mol% of Cul). A variety of aryl iodides could he aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.展开更多
文摘Acrylonitrile reacts with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound arsine palladium(0) complex to afford stereoselectively (E)-cinnamo- nitriles in high yields.
基金This work was supported by the Natural Science Foundation of Jiangxi Province.
文摘Arylation of acrylamide and acrylonitrile were carried out with various arenediazonium tetrafluoroborates in the presence of a catalytic amount of Pd(OAc)(2) in ethanol and a variety of substituted (E)-cinnamamides and (E)-cinnamonitriles were obtained in high yields under mild reaction conditions.
文摘Allyl and cinnamyl and propargyl bromide reacted under mild conditions with triarylbismuth under catalysis by Pd(O) to give 3-arylpropenes, 1, 3-diarylpropenes and arylpropadienes in modest to excellent yields.
基金Supported by Natural Science Foundation of Zhejiang Province
文摘(?)-Aryl-(?)-cyanosulfones are prepared under mild conditions with good yields by using palladium-catalyzed coupling reaction between aryl halides and (?)-cyanosulfones in the presence of phase transfer catalyst.
基金We gratefully acknowledge financial support from the National Science of Foundation of China(81960631)the Yunnan Fundamental Research Project(202001AS070038)+1 种基金the Top Young Talent of Ten Thousand Talents Program of Yunnan Province(R.Zhan and L.-D Shao)the Start-up Fund of Yunnan University of Chinese Medicine(2019YZG03).
文摘α-C(sp^(3))-H arylation is an important type of C-H functionalization.Various biologically significant natural products,chemi-cal intermediates,and drugs have been effectively prepared via C-H functionalization.Cyclic carbonyl compounds comprise of cyclic ketones,enones,lactones,and lactams.Theα-C(sp^(3))-H arylation of these compounds have been exhibited high efficiency in forming C(sp^(3))-C(sp^(2))bonds,played a crucial role in organic synthesis,and attracted majority of interests from organic and medicinal communities.This review focused on the most significant advances including methods,mechanism,and applications in total synthesis of natural products in the field ofα-C(sp^(3))-H arylations of cyclic carbonyl compounds in recent years.
文摘Allylic alcohols react with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound bidentate sulfur palladium (0) complex to form 3-arylaldehydes or ketones in good yields.
基金supported by the National Natural Science Foundation of China(22001065)the Science and Technology Foundation of Hunan Province(2021JJ30090)+3 种基金Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)Shenzhen Science and Technology Program(KQTD20210811090112004)supported by Center for Computational Science and Engineering at SUSTechthe CHEM high-performance supercomputer cluster(CHEM-HPC)located at the Department of Chemistry,SUSTech。
文摘The conversion of commercially available chiral sulfinamides into pharmaceutically useful chiral sulfoximines via direct SIVfunctionalization is synthetically attractive but challenging due to the competitive reaction of N-functionalization. Herein, we disclose a novel strain-release strategy to access stereospecific and chemoselective SIV-arylation and alkenylation of sulfinamides using arynes and strained cyclic alkynes. This method tolerates an unprecedented chemical diversity of functional groups attached to the nitrogen center(N-R). The origin of the high SIV-selectivity is elucidated by density functional theory calculations, suggesting a stepwise mechanism for the aryne substrates and a concerted mechanism for the cyclic alkynes.
基金The National Natural Science Foundation of China(No.22169009)Jiangxi Provincial Natural Science Foundation(No.20212ACB204007)Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(20212BCD42018)are appreciated for financial support。
文摘The rapid synthesis of structurally complicated electron donors&acceptors still remains a major challenge in organic solar cells(OSC).In this work,we developed a highly efficient strategy to access long-chain oligomeric donor and acceptors for OSC applications.A series of cyclopentadithiophene(CPDT)and benzothiadiazole(BT)-basedπ-conjugated oligomers,i.e.,three oligomeric acceptors(BTDT)n-IC(n=1—3)and one long-chain oligomeric donor(BTDT)4-RD,are facilely synthesized by an atom-and step-economical,and labor-saving direct C—H arylation(DACH)reaction(i.e.,C—H/C—Br cross coupling).Note that(BTDT)4-RD involving five CPDT,four BT and two rhodamine(RD)building blocks is the longest oligomeric donor in the fullerene-free OSC devices ever reported.The dependence of the structure-property-performance correlation of(BTDT)n-IC(n=1—3)and(BTDT)4-RD on theπ-conjugation lengths is thoroughly investigated by opto-electrochemical measurements,bulk heterojunction(BHJ)OSC devices and microscopies.The(BTDT)1-IC:PBDB-T and(BTDT)4-RD:Y6 BHJs achieve power conversion efficiencies of 9.14%and 4.51%,respectively.Our findings demonstrate that DACH reaction is a powerful tool to tune the opto-electronic properties and device performances by regulating the lengths ofπ-conjugated oligomers with varied numbers of repeating units.
基金support from the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2017124)。
文摘We report the unprecedent Pd(I)catalyzed ring-opening arylation of cyclopropyl-α-aminoamides.This protocol allows facile access to biologically important α-ketoamide-containing oligopeptides and even more challenging peptide-natural product conjugates.Site selectivity was achieved by introduction of special unnatural amino acids,which also meets the requisite of bioorthogonal chemistry.Mechanism investigations reveals a distinct domino radical ring-opening process through Pd(I)catalysis.
基金supported by the National Key Research and Development Program of China(No.2018YFA0704502)the National Natural Science Foundation of China(Nos.21871261,21931011)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZZ105).
文摘Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β-aryl esters has been disclosed,using the native amino as the directing group.A variety of chiralα-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono-and di-arylated products.
基金This work was financially supported by the National Key R&D Program of China(2021YFA0717900)National Natural Science Foundation of China(no.51933008,22222506 and 52121002).
文摘Direct arylation polycondensation(DArP)has emerged as an eco-friendly and atom-efficient methodology for the syntheses ofπ-conjugated polymers(CPs).This approach features the direct C—H arylation of an aromatic hydrocarbon with an aryl halide.Given the prevalence of thiophene-containing CPs,achieving efficient and defect-free DArP of thiophene-based C−H monomers is of great significance.This review presents a mechanistic insight into DArP and describes the development of DArP catalytic systems for varied thiophene-based C−H monomers.Moreover,the control of the primary defects(i.e.,branching and homo-coupling)in thiophene-based DArP is also elaborated.By emphasizing the principles behind monomer selection and catalytic system optimization,this review intends to provide a framework for future advancements in the DArP of thiophene-containing CPs.
基金financially supported by the National Natural Science Foundation of China(Nos.51933008 and 52121002)the Fundamental Research Funds for the Central Universities。
文摘The solubility of a direct arylation polycondensation(DArP)synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorothien-2-yl)ethene)(PFuD PP-4FTVT),in variou s organic solvents was studied.The polymer is soluble in 3-methylcyclohexanone(3-MC),a green solvent from peppermint oil,besides other solvents such as anisole,cyclopentyl methyl ether(CPME)and o-dichlorobenzene(o-DCB),etc.Based on the Hansen solu bility parameters(HSP)analysis,3-MC is identified as a"marginal solvent"of PFuDPP-4FTVT.The morphology of the spin-coated films with 3-MC as the solvent strongly correlated with the solution preparation conditions.With a 3-MC solution aged for 3 h at 70℃,n-channel organic thin-film transistors(OTFTs)with electron mobility(μe)above 1 cm^(2)·V^(-1)·s^(-1) and current on/off ratio(Ion/Ioff)higher than 105 were fabricated by spin-coating.This is the first report on high mobility conjugated polymers for OTFTs processible with natu rally occurred green solvent.
基金the National Natural Science Foundation of China(No.51773046)the Fundamental Research Funds for the Central Universities,the School of Materials Science and Engineering,Shaanxi Normal Universitythe Project of Key Laboratory of Organic Synthesis of Jiangsu Province,College of Chemistry Chemical Engineering and Materials Science,Soochow University。
文摘As the high calibre candidate of lightweight and flexible solar cells,polymer solar cells(PSCs)have made tremendous progress in recent years.However,the active photovoltaic materials in PSCs are mainly synthesized by metal-mediated coupling reaction requiring harsh reaction conditions,multiple-step synthesis,and cumbersome purification,which is not cost-efficient and may bring toxicity concerns.It is not favorable to the production of photovoltaic polymers and PSC devices on a large scale,and therefore unsuitable for the PSCs industrialization.Direct arylation coupling reaction via aromatic C―H bonds activation enables the synthesis of conjugated polymers under mild conditions and simultaneously reduces synthetic steps,difficulty,and toxic reaction byproducts.This review provides an overview of the history of preparing representative photovoltaic polymers utilized in PSCs through direct arylation reactions and discusses the activity and selectivity of C―H bonds in typical building blocks under different reaction conditions.Especially,the impact of direct arylation condition on defect formation and photovoltaic performance of the photovoltaic polymers is addressed and compared with conventional Stille coupling methods.
基金financially supported by the National Key R&D Program of “Strategic Advanced Electronic Materials” (No. 2016YFB0401101) of the Chinese Ministry of Science and Technologythe National Natural Science Foundation of China (No. 51333006)
文摘A highly efficient and eco-friendly protocol for the synthesis of an alternating copolymer poly(7,7'-diazaisoindigo-alt-(E)-1,2- bis(3,4-difluorothien-2-yl)ethene)(PAIID-4FTVT) via direct arylation polycondensation (DArP) is presented. Through detailed study, we found that the inhibitory effect of 7,7'-diazaisoindigo on DArP stemmed from the coordination of N atom with catalyst can be overcome by using dimethylacetamide (DMAc) as the co-solvent. Thus, PAIID-4FTVT with number-average molecular weight (Mn)>100kDa was synthesized via DArP by optimizing the content of DMAc. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy revealed that PAIID-4FTVT was defect-free. Top gate and bottom contact (TG/BC) organic thin-film transistors (OTFTs) were fabricated to characterize the semiconducting properties of the polymers. PAIID-4FTVT displayed unipolar n-type characteristics with the electron mobility (μe) strongly dependent on Mn. The highest μe up to 0.25 cm^2·V^-1 s^-1 was achieved with the high molecular weight sample.
基金We gratefully thank the National Natural Science Foundation of China (No. 31071720) for generous fi- nancial support.
文摘A general and efficient Cu(II)-catalyzed cross-coupling method is reported for the preparation of acyclic tertiary amides. Generally moderate to excellent yields and functional group tolerance were obtained with secondary acyclic amides and aryl halides as substrates in toluene.
基金supported by the National Natural Science Foundation of China (No.21102036)Plan for Scientific Innovation Talent of Henan University of Technology (No.11CXRC02)startup fund from HAUT (No.2010BS042)
文摘10 mol% Cul combined with the DMEDA ligand can efficiently catalyze the N-arylation of 2-arylindoles with aryl iodides and aryl bromides in good to excellent yields. The aryl halides bearing electron-rich or electron-deficient functional groups can be well tolerated under this mild reaction conditions.
基金supported by the National Natural Science Foundation of China(21502098,21672105,21725204,91753124)Natural Science Foundation of Tianjin(17JCYBJC19700,18JCZDJC32800)+1 种基金Qingdao National Laboratory for Marine Science and Technologythe State Key Laboratory of Elemento-Organic Chemistry at Nankai University
文摘PAD4 is a promising epigenetic drug target for various cancers and immune diseases. In this work, we applied a Cu-catalyzed C–H arylation reaction of N-heteroarene to the synthesis of complex non-covalent PAD4 inhibitors bearing a bi-heteroaryl pharmacophore. This strategy allowed us to access various analogs of C_2-aryl substituted benzimidazoles from a common benzimidazole core and easily accessible aryl iodides. Preliminary SAR studies revealed the indole motif of GSK-484 is critical to its activity. Replacing the N-cyclopropylmethyl group to N-benzyl group on the indole ring of GSK-484 resulted in more than5-fold increase in cell killing efficacy against 4T1 cell line.
基金financial support from the National Natural Science Foundation of China(No.21276043)
文摘We report a practical and highly efficient protocol for the arylation of pyridine N-oxides with arylboronic acid through palladium-catalyzed Suzuki reaction in water.This ligand-free Suzuki reaction is performed in the presence of diisopropylamine and gives 2-or 3-arylated pyridyl N-oxide derivatives in good to excellent yields within 1 h.
基金financially supported by the National Natural Science Foundation of China(Nos.21674060 and 51603123)。
文摘Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs)and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT)for new donor-acceptor conjugated polymers.The polymers exhibited blue hues in neutralstate with distinct color-to-transmissive reversible electrochromic switching under applied potentials from 0 V to+1.5 V,and showed high coloration efficiencies(436-438 cm^(2)·C^(-1))in near-infrared regions with high switching speeds around 1-2 s under ambient conditions.
基金supported fnancially by the National Basic Research Program of China(973 Program,No.2012CB722603)the Start-Up Foundation for Young Scientists of Shihezi University(Nos.RCZX201012,RCZX201014,RCZX201015)
文摘Tetrazole-l-acetic acid was found to serve as a superior ligand for Cul-catalyzed N-arylation of imidazoles with aryl iodides under a low catalyst loading (5 mol% of Cul). A variety of aryl iodides could he aminated to provide the N-arylated products in good to excellent yields without the need of an inert atmosphere.