A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, ...A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, 10, 14,18)] were synthesized. All of these amphiphilic europium(III) complexes could form stable Langmuir film at air/water interface and could be transferred onto hydrophilic quartz and mica substrates by measurement of UV spectra in which the absorbance of the LB films at about 288 nm scales showed the linearity with the number of layers deposited. In order to investigate relation between fluorescence properties and the arrangement of molecular in LB films, surface topography of monolayer films were observed by atomic force microscopy (AFM). Results showed that the emission spectra have Eu(III) characteristic peaks and strong emission strength. It is interesting that the molecular with looser arrangement in LB films has better monochromacity, which illustrated that energy might transferred more easily from ligand to Eu(III) in loosen structure films.展开更多
Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity ...Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity of the substrate by causing directional adsorption.However,scalable and efficient techniques for using EEFs as“smart catalysts”have been lacking,hindering their application.In this study,we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer(EDL)theory.This approach led to moderate to good yields of the corresponding C7-thiocyanation products.DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones,allowing the C7-thiocyanation to proceed via a radical reaction mechanism.Additionally,the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties.Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.展开更多
A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplic...A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplicity,mild reaction conditions with blue LED light employing Ru(bpy)3Cl2.6H2O as a photoredox catalyst,a combination of O2 from air and Cu(OAc)2 as the oxidant and broad substrate applicability.展开更多
Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides....Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.展开更多
A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles ...A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles via the selectivity of suitable cyclization partners.This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and excellent regioselectivity.展开更多
A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivit...A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivity,broad substrate scope and high step economy,which would provide the refe rence for the construction of the fused 4-aminoquinazolines with biologically and pharmacologically active compounds.展开更多
A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent a...A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation.Molecular oxygen in the air acts as an oxidant.3,3’-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions.No any catalyst and additive were required.N2 and water were released as sole by-products.Absence of water and fluorinated alcohol resulted in Wolff rearrangement product.展开更多
A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano sou...A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano source via N-O bond cleavage and fragmentation.Variously substituted(especially 6-or 7-substituted)quinolines could be easily afforded.This procedure features wide functional group compatibility,efficiency and avoiding toxic cyano source.Meanwhile,this protocol could be successfully applied to scale-up synthesis.Further chemical transformations of 3-cyanoquinoline could give some valuable skeletons,demonstrating its potential in synthetic application.展开更多
Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional g...Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.展开更多
文摘A series of europium(III) complexes with different chain length, tris [2-m-pyridylmethanamido-5-phenyl- (1,3,4)-oxadiazole] mono [2-(4-n-alkylphenyl)-iminazole (4,5-f)-1,10-phenanthroline] Eu(III) [Eu(PMA)3Nn (n = 6, 10, 14,18)] were synthesized. All of these amphiphilic europium(III) complexes could form stable Langmuir film at air/water interface and could be transferred onto hydrophilic quartz and mica substrates by measurement of UV spectra in which the absorbance of the LB films at about 288 nm scales showed the linearity with the number of layers deposited. In order to investigate relation between fluorescence properties and the arrangement of molecular in LB films, surface topography of monolayer films were observed by atomic force microscopy (AFM). Results showed that the emission spectra have Eu(III) characteristic peaks and strong emission strength. It is interesting that the molecular with looser arrangement in LB films has better monochromacity, which illustrated that energy might transferred more easily from ligand to Eu(III) in loosen structure films.
基金supported by the National Natural Science Foundation of China(21172200,21302172)the Basic Research Training Project of Zhengzhou University(JC2020053021)supported by the National Research Foundation of Korea(CRI Project No.2018R1A3B1052702 for Jong Seung Kim)。
文摘Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity of the substrate by causing directional adsorption.However,scalable and efficient techniques for using EEFs as“smart catalysts”have been lacking,hindering their application.In this study,we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer(EDL)theory.This approach led to moderate to good yields of the corresponding C7-thiocyanation products.DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones,allowing the C7-thiocyanation to proceed via a radical reaction mechanism.Additionally,the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties.Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.
基金We acknowledge partial financial support from the Ministry of Science and Technology of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)and Zhengzhou University。
文摘A visible-light-promoted formal[2+2+1]cyclization of N-aryl glycines with quinoxalin-2(1H)-ones to synthesize tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones have been developed.The protocol features operational simplicity,mild reaction conditions with blue LED light employing Ru(bpy)3Cl2.6H2O as a photoredox catalyst,a combination of O2 from air and Cu(OAc)2 as the oxidant and broad substrate applicability.
基金We are grateful to the National Natural Science Foundation of China,the Education Department of Henan Province science and technology research projects (No.13A150681) for financial support of this research
基金partial financial support from the Ministry of Science and Technology of China (No. 2016YFE0132600)Zhengzhou University
文摘Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.
基金partial financial support from the Ministry of Science and Technology of China(No.2016YFE0132600)Zhengzhou University。
文摘A selective ring-opening [3+2] cyclization reaction of benzo[d]isoxazoles with 2-bromo-propanamides has been developed.The azaoxyallyl cation intermediates are employed as C^O 3-atom synthon to build oxa-heterocycles via the selectivity of suitable cyclization partners.This transformation provides rapid access to highly functionalized 2-hydroxyaryl-oxazolines under mild conditions and excellent regioselectivity.
基金financial support from the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)Zhengzhou University。
文摘A novel approach for the synthesis of 4-aminoquinazolines has been developed via rhodium(Ⅲ)-catalyzed [4+2] annulation of N-arylbenzamidines with 1,4,2-dioxazol-5-ones.This reaction features excellent regioselectivity,broad substrate scope and high step economy,which would provide the refe rence for the construction of the fused 4-aminoquinazolines with biologically and pharmacologically active compounds.
基金financial support from the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No. GZS2020001)+1 种基金National Innovation and Entrepreneurship Training Program for College students (No.201910459064)Zhengzhou University
文摘A green tandem reaction,including insertion/aerobic oxidation/bisindolylation,starting from indoles and diazo compounds has been developed.The combination of water and fluorinated alcohol plays dual roles as solvent and promoter in this chemical transformation.Molecular oxygen in the air acts as an oxidant.3,3’-Bis(indolyl)methanes with quaternary carbon were produced under metal-free conditions.No any catalyst and additive were required.N2 and water were released as sole by-products.Absence of water and fluorinated alcohol resulted in Wolff rearrangement product.
基金partial financial support from the National Key R&D Program of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)Key Scientific and Technological Project of Henan Province(No.212102311068)。
文摘A Ru(Ⅲ)-catalyzed annulation reaction of 2-aminoaromatic aldehydes(ketones)and isoxazoles to afford diverse 3-cyanoquinolines has been developed.Notably,isoxazole acted as a cyclization reagent and nontoxic cyano source via N-O bond cleavage and fragmentation.Variously substituted(especially 6-or 7-substituted)quinolines could be easily afforded.This procedure features wide functional group compatibility,efficiency and avoiding toxic cyano source.Meanwhile,this protocol could be successfully applied to scale-up synthesis.Further chemical transformations of 3-cyanoquinoline could give some valuable skeletons,demonstrating its potential in synthetic application.
基金the Ministry of Science and Technology of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)。
文摘Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.