Herein,we developed a tertiary amine-catalyzed stereoretentive multi-component cascade reaction featuring an amidation/[4+1]annulation/decarboxylation/Curtius rearrangement/[2+n]annulation sequence.This metal-free and...Herein,we developed a tertiary amine-catalyzed stereoretentive multi-component cascade reaction featuring an amidation/[4+1]annulation/decarboxylation/Curtius rearrangement/[2+n]annulation sequence.This metal-free and step-economic method provided a broad range of cyclic ureas/urethanes in green solvent under mild conditions without employing explosive and toxic reagents.Importantly,this reaction generated isocyanates in situ under catalytic conditions via a decarboxylation/Curtius rearrangement process of dioxazolones.展开更多
A novel protocol for the preparation of highly functionalized 2-azabicyclo[3.3.1]nonane(morphan)derivatives via a multicomponent cascade reaction,involving 3-formylchromones,2-naphthols,and enaminones in the ionic liq...A novel protocol for the preparation of highly functionalized 2-azabicyclo[3.3.1]nonane(morphan)derivatives via a multicomponent cascade reaction,involving 3-formylchromones,2-naphthols,and enaminones in the ionic liquid[BMIM]PF6 as the solvent and promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU),was developed,which involved the cleavage of one C–O bond and formation of four bonds(1 C–O,1 C–N,and 2 C–C bonds).As a result,a series of morphan derivatives were produced through a cascade reaction,including a sequence of 1,2-addition,enol-keto tautomerization,Michael addition,dehydration,another Michael addition,imine-enamine tautomerization,and N-alkylation reactions,which were accompanied by a ring-opening reaction.This protocol was suitable for combinatorial and parallel syntheses of natural product-like morphan compounds in a one-pot reaction rather than through tedious multi-step reactions.展开更多
A novel synthesis of C2-spiroindoline derivatives based on the cascade reaction of 2-aryl-3H-indoles with cyclo- propanols is presented. The formation of product involves Rh(III)-catalyzed aryl C(sp2)—H bond alkylati...A novel synthesis of C2-spiroindoline derivatives based on the cascade reaction of 2-aryl-3H-indoles with cyclo- propanols is presented. The formation of product involves Rh(III)-catalyzed aryl C(sp2)—H bond alkylation of 2-aryl- 3H-indole, which is followed by intramolecular spiroannulation. In this tandem process, cyclopropanol acts as not only an alkylating agent but also a masked nucleophile to take part in the construction of the spirocyclic scaffold. Meanwhile, air acts as an economical and sustainable oxidant to promote the regeneration of the active catalyst. By using this method, hybrid compounds containing the central scaffolds of some clinical drugs were prepared effectively. In general, this newly developed method has advantages such as easily obtainable substrates, concise synthetic procedure, excellent atom-economy, good compatibility with diverse functional groups and ready scalability.展开更多
Wound healing in diabetic patients presents significant challenges due to heightened risks of bacterial infection,elevated glucose levels,and insufficient angiogenesis.Nanozymes are widely employed for wound healing,b...Wound healing in diabetic patients presents significant challenges due to heightened risks of bacterial infection,elevated glucose levels,and insufficient angiogenesis.Nanozymes are widely employed for wound healing,but most current nanozyme systems exhibit only moderate activity limited by incompatible reaction microenvironments including p H and hydrogen peroxide(H_(2)O_(2))concentration.Herein,a glucoseactivated nanozyme hydrogel was developed using bovine serum albumin(BSA)-modified gold nanoparticles(Au NPs)attached to a two-dimensional(2D)metal-organic framework(MOF)(Cu-TCPP(Fe)@Au@BSA)by an in situ growth method.The Au NPs function as a glucose oxidase(GOx)-like enzyme,converting glucose to gluconic acid and H_(2)O_(2),triggering the peroxidase(POD)-like activity of Cu-TCPP(Fe)to produce hydroxyl radicals(·OH),effectively eliminating bacteria.Additionally,the modification of BSA reduces the Au NP size,enhancing enzyme activity.Both in vitro and in vivo tests demonstrate that this nanozyme hydrogel can be activated by the microenvironment to lower blood glucose,eliminate bacterial infections,and promote epithelial formation and collagen deposition,thus accelerating diabetic wound healing effectively.The multifunctional nanozyme hydrogel dressing developed in this study presents a promising therapeutic approach to enhance diabetic wound healing.展开更多
A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated...A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated imine(-CH=N-)groups and a cobalt-based MOFs(Co-hmta)structure prepared using hydrogen bonding stacking with hexamethylenetetramine(hmta)as the organic ligand.Subsequently,the Co-hmta@La-salen composite was chosen as a template for the pyrolysis process to synthesize a La(OH)_(3)supported metallic Co catalyst incorporating carbon-nitrogen(Co/La(OH)_(3)-CNhmta)catalyst.The catalytic results show that Co/La(OH)_(3)-CN-hmta(54%and 46%selectivity for aniline and N-phenylbenzylamine,respectively)displays superior cascade performance compared to classic Co/La(OH)_(3)-CN-nit catalyst(69%and 31%selectivity for aniline and N-phenylbenzylamine,respectively).Moreover,the kinetic test results indicate that N-alkylation is the rate-limiting step of the overall cascade reaction.The Co/La(OH)_(3)-CN-hmta catalyst can be separated from the reaction system using a magnet,and it also exhibits good cyclic stability.All of these suggest that the“MOFs plus MOFs via coordination”templating method can be employed as an efficient strategy for the preparation of supported catalysts.展开更多
An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a...An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a simple synthetic method for N-aryl indoles.展开更多
1-Indenones are important scaffolds in natural products, biologically active molecules as well as functional materials. Recently, radical cascade cyclization has emerged as an efficient and powerful strategy for the c...1-Indenones are important scaffolds in natural products, biologically active molecules as well as functional materials. Recently, radical cascade cyclization has emerged as an efficient and powerful strategy for the construction of valuable and versatile functionalized 1-indenones. In this review, the recent advances of this rapidly growing area were summarized. The selected examples have been classified according to the type of reaction substrates such as 1,3-diarylpropynones, 2-alkynylbenzonitriles, arylpropynols, 1,5-enynes and 2-alkynylated bromocinnamates.展开更多
An efficient and novel procedure for the preparation of pyrazolo[3,4-b]pyridine derivatives through multi-component reaction of aldehyde, 5-amino-3-methyl-1-phenylpyrazole and malononitrile or cyanoacetate in [bmim][B...An efficient and novel procedure for the preparation of pyrazolo[3,4-b]pyridine derivatives through multi-component reaction of aldehyde, 5-amino-3-methyl-1-phenylpyrazole and malononitrile or cyanoacetate in [bmim][BF4] is described in this paper. Advantages of the method presented here include mild conditions, high yields together with a green nature and ease of recovery and reuse of the reaction medium.展开更多
We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe ...We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe showed good selectivity and high sensitivity towards H2S and it was capable of detecting and imaging H2S in living HeLa cells, indicating its potential biological applications.展开更多
A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol...A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.展开更多
Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-m...Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-modality fluorescent probe COU-DPA-1 for selective detection, differentiation, and detoxification of multiple heavy metal ions(Ag^(+), Hg^(2+), Cu^(2+)). The probe shows divergent fluorescence(FL)/circular dichroism(CD) responses via divergent bond-cleavage cascade reactions(metal ion promoted C-S cleavage and hydrolysis at two distinctive cleavage sites): FL “turn-off” and CD “turn-on” for Ag+(no hydrolysis), FL “turn-on” and CD “turn-off” for Hg^(+)(imine hydrolysis), and FL “self-threshold ratiometric” and CD “turn-off” for excess Cu^(2+)(lactone and imine hydrolysis), providing the first example of a fluorescence/CD dual-modality probe for multiple species with complimentary responses. Moreover, the bond-cleavage cascade reactions also lead to the formation of D-penicillamine heavy metal ion complexes for potential detoxification treatments.展开更多
A mild and efficient photochemical multi-component tandem reaction of quinoxalin-2(1H)-ones, alkenes and sulfinic acids is reported. This tandem reaction could be conveniently carried out at room temperature by employ...A mild and efficient photochemical multi-component tandem reaction of quinoxalin-2(1H)-ones, alkenes and sulfinic acids is reported. This tandem reaction could be conveniently carried out at room temperature by employing 4Cz IPN as the metal-free photocatalyst and dioxygen(air) as the environmentally benign oxidant. A number of sulfonated quinoxalin-2(1H)-ones were obtained in satisfactory yields with favorable functional group tolerance. Radical trapping experiment and fluorescence quenching experiments were performed to elucidate this visible-light mediated radical reaction process.展开更多
A simple synthesis of highly functionalized 2,5-diaminofurans based pyrimidine derivatives from 1-（carboxymethyl）uracil via a multi-component reaction is described. The reactive 1：1 intermediate produced from the r...A simple synthesis of highly functionalized 2,5-diaminofurans based pyrimidine derivatives from 1-（carboxymethyl）uracil via a multi-component reaction is described. The reactive 1：1 intermediate produced from the reaction of tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped at room temperature by 1-（carboxymethyl）uracil derivatives to yield polyfunctio- nalized furan rings in fairly good yields.展开更多
Organoselenium and pyrazole compounds are important scaffolds in pharmaceutical molecules.Herein,an electrochemical multicomponent one-pot cascade reaction of hydrazide,pentane-2,4-diones and diselenides has been esta...Organoselenium and pyrazole compounds are important scaffolds in pharmaceutical molecules.Herein,an electrochemical multicomponent one-pot cascade reaction of hydrazide,pentane-2,4-diones and diselenides has been established to construct 4-selenylacylpyrazoles.It is worth noting that for this efficient and green protocol,neither metal catalysts nor external oxidants are required.Moreover,this process exhibits step economy,ease of scale up and high yields to deliver various 4-selenylacylpyrazoles.展开更多
An N-heterocyclic carbene(NHC)-catalysed retro-aldol/aldol cascade reaction of spirooxindole-basedβ-hydroxyaldehyde has been developed.The ring opening-closure process enables the diastereodivergent synthesis of spir...An N-heterocyclic carbene(NHC)-catalysed retro-aldol/aldol cascade reaction of spirooxindole-basedβ-hydroxyaldehyde has been developed.The ring opening-closure process enables the diastereodivergent synthesis of spirocyclopentaneoxindole products with four consecutive stereocenters by simply changing the reaction solvents(THF or DCE).The Michael/aldol/retro-aldol/aldol sequential protocol allows the diastereodivergent synthesis of spirocyclopentaneoxindoles from 3-substituted oxindole andα,β-unsaturated aldehyde under the relay catalysis of a chiral secondary amine and an NHC catalyst.Moreover,four stereoisomers of the product can be selectively provided by using different combinations of a chiral secondary amine and a solvent.展开更多
Oxonium ylide intermediates generated from α-diazocarbonyl compounds and water were trapped by Zn（Ⅱ）-activated α- dicarbonyl compounds. The reaction gave α,β-dihydroxyl acid derivatives in moderate yield.
The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H in...The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H insertion process.Deuterium labelling experiments,kinetic studies and control experiments were carried out for the rationalization of the mechanism.展开更多
Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecula...Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.展开更多
A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficie...A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature.This metal-free visiblelight-driven tandem reaction was conducted through proton-coupled electron transfer(PCET)process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene(4CzIPN)as the photocatalyst.展开更多
Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natura...Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natural nicotinamide adenine dinucleotide(NADH)oxidase(NOX),a novel and efficient single-atom rhodium catalyst(Rh1/NC)was developed to mimic NOX.The Rh_(1)/NC demonstrated the ability to catalyze the dehydrogenation of NADH and transfer electrons to O_(2)to generate H_(2)O_(2)through the typical two-electron pathway.Furthermore,our findings revealed that Rh_(1)/NC exhibits the ability to catalyze the conversion of produced H_(2)O_(2)into OH under mildly acidic conditions.This process amplifies the oxidation of NADH,showcasing NADH peroxidase-like activity(NPx-like).As a paradigm,this unique dual enzyme-like property of Rh_(1)/NC with a positive feedback effect holds significance in disrupting cancer cellular homeostasis.Rh_(1)/NC can effectively consume NADH via cascade biocatalytic reactions within cancer cells,further triggering the elevation of reactive oxygen species(ROS),leading to impaired oxidative phosphorylation and decreased mitochondrial membrane potential,thus damaging the adenosine triphosphate(ATP)synthesis.The resulting'domino effect'interferes with the energy metabolism homeostasis of cancer cells,ultimately promoting cell apoptosis.This study provides potential guidance for the rational design of materials with greater capabilities.展开更多
基金financial support provided by the National Natural Science Foundation of China(22207063)111 Project(D20015),Hubei Provincial Central Government Guided Local Science and Technology Development Project(2024BSB016)+1 种基金Natural Science Research Project of Yichang City(A23-2-002)the Opening Funding of Hubei Key Laboratory of Natural Products Research and Development,China Three Gorges University(2024NPRD03,2024NPRD04,2024NPRD05).
文摘Herein,we developed a tertiary amine-catalyzed stereoretentive multi-component cascade reaction featuring an amidation/[4+1]annulation/decarboxylation/Curtius rearrangement/[2+n]annulation sequence.This metal-free and step-economic method provided a broad range of cyclic ureas/urethanes in green solvent under mild conditions without employing explosive and toxic reagents.Importantly,this reaction generated isocyanates in situ under catalytic conditions via a decarboxylation/Curtius rearrangement process of dioxazolones.
基金We are grateful for financial support from the Natural Science Foundation of Yunnan Province,China(No.2019FY003003)the Scientific and Technological Innovation Team of Green Synthesis and Activity Research of Natural-like Heterocyclic Compound Libraries in Universities of Yunnan Province(No.C17624011121).The authors thank the Advanced Analysis and Measurement Center of Yunnan University for the sample testing service.
文摘A novel protocol for the preparation of highly functionalized 2-azabicyclo[3.3.1]nonane(morphan)derivatives via a multicomponent cascade reaction,involving 3-formylchromones,2-naphthols,and enaminones in the ionic liquid[BMIM]PF6 as the solvent and promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU),was developed,which involved the cleavage of one C–O bond and formation of four bonds(1 C–O,1 C–N,and 2 C–C bonds).As a result,a series of morphan derivatives were produced through a cascade reaction,including a sequence of 1,2-addition,enol-keto tautomerization,Michael addition,dehydration,another Michael addition,imine-enamine tautomerization,and N-alkylation reactions,which were accompanied by a ring-opening reaction.This protocol was suitable for combinatorial and parallel syntheses of natural product-like morphan compounds in a one-pot reaction rather than through tedious multi-step reactions.
文摘A novel synthesis of C2-spiroindoline derivatives based on the cascade reaction of 2-aryl-3H-indoles with cyclo- propanols is presented. The formation of product involves Rh(III)-catalyzed aryl C(sp2)—H bond alkylation of 2-aryl- 3H-indole, which is followed by intramolecular spiroannulation. In this tandem process, cyclopropanol acts as not only an alkylating agent but also a masked nucleophile to take part in the construction of the spirocyclic scaffold. Meanwhile, air acts as an economical and sustainable oxidant to promote the regeneration of the active catalyst. By using this method, hybrid compounds containing the central scaffolds of some clinical drugs were prepared effectively. In general, this newly developed method has advantages such as easily obtainable substrates, concise synthetic procedure, excellent atom-economy, good compatibility with diverse functional groups and ready scalability.
基金supported by the National Natural Science Foundation of China Project(No.22208321)the China Postdoctoral Science Foundation Project(No.2022M720130)+1 种基金the Key Scientific Research Project of Henan Province High Education Institutions(No.24A350018)the Natural Science Foundation of Henan Province-Outstanding Youth Foundation(No.232300421058)。
文摘Wound healing in diabetic patients presents significant challenges due to heightened risks of bacterial infection,elevated glucose levels,and insufficient angiogenesis.Nanozymes are widely employed for wound healing,but most current nanozyme systems exhibit only moderate activity limited by incompatible reaction microenvironments including p H and hydrogen peroxide(H_(2)O_(2))concentration.Herein,a glucoseactivated nanozyme hydrogel was developed using bovine serum albumin(BSA)-modified gold nanoparticles(Au NPs)attached to a two-dimensional(2D)metal-organic framework(MOF)(Cu-TCPP(Fe)@Au@BSA)by an in situ growth method.The Au NPs function as a glucose oxidase(GOx)-like enzyme,converting glucose to gluconic acid and H_(2)O_(2),triggering the peroxidase(POD)-like activity of Cu-TCPP(Fe)to produce hydroxyl radicals(·OH),effectively eliminating bacteria.Additionally,the modification of BSA reduces the Au NP size,enhancing enzyme activity.Both in vitro and in vivo tests demonstrate that this nanozyme hydrogel can be activated by the microenvironment to lower blood glucose,eliminate bacterial infections,and promote epithelial formation and collagen deposition,thus accelerating diabetic wound healing effectively.The multifunctional nanozyme hydrogel dressing developed in this study presents a promising therapeutic approach to enhance diabetic wound healing.
基金Project supported by the Natural Science Foundation of Jiangsu Province (BK20210066)Natural Science Foundation of Heilongjiang Province (ZD2022E007).
文摘A composite metal-organic frameworks(MOFs)structure,designated as Co-hmta@La-salen,was synthesized through coordination interactions between a one-dimensional lanthanum MOFs(La-salen)with high density of uncoordinated imine(-CH=N-)groups and a cobalt-based MOFs(Co-hmta)structure prepared using hydrogen bonding stacking with hexamethylenetetramine(hmta)as the organic ligand.Subsequently,the Co-hmta@La-salen composite was chosen as a template for the pyrolysis process to synthesize a La(OH)_(3)supported metallic Co catalyst incorporating carbon-nitrogen(Co/La(OH)_(3)-CNhmta)catalyst.The catalytic results show that Co/La(OH)_(3)-CN-hmta(54%and 46%selectivity for aniline and N-phenylbenzylamine,respectively)displays superior cascade performance compared to classic Co/La(OH)_(3)-CN-nit catalyst(69%and 31%selectivity for aniline and N-phenylbenzylamine,respectively).Moreover,the kinetic test results indicate that N-alkylation is the rate-limiting step of the overall cascade reaction.The Co/La(OH)_(3)-CN-hmta catalyst can be separated from the reaction system using a magnet,and it also exhibits good cyclic stability.All of these suggest that the“MOFs plus MOFs via coordination”templating method can be employed as an efficient strategy for the preparation of supported catalysts.
基金supported by the Intercollegiate Key Scientific Research Projects of Henan Province(15A150018)~~
文摘An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a simple synthetic method for N-aryl indoles.
基金the financial support from the National Natural Science Foundation of China(No.21501010)Key Research Projects of Universities in Henan Province(No. 19A350011)+1 种基金2017 Science and Technology Innovation Team in Henan Province(No. 22120001)Major Scientific and Technological Projects in Henan Province(No. 181100310500)
文摘1-Indenones are important scaffolds in natural products, biologically active molecules as well as functional materials. Recently, radical cascade cyclization has emerged as an efficient and powerful strategy for the construction of valuable and versatile functionalized 1-indenones. In this review, the recent advances of this rapidly growing area were summarized. The selected examples have been classified according to the type of reaction substrates such as 1,3-diarylpropynones, 2-alkynylbenzonitriles, arylpropynols, 1,5-enynes and 2-alkynylated bromocinnamates.
基金the National Natural Science Foundation of China(No.20573034).
文摘An efficient and novel procedure for the preparation of pyrazolo[3,4-b]pyridine derivatives through multi-component reaction of aldehyde, 5-amino-3-methyl-1-phenylpyrazole and malononitrile or cyanoacetate in [bmim][BF4] is described in this paper. Advantages of the method presented here include mild conditions, high yields together with a green nature and ease of recovery and reuse of the reaction medium.
基金financially supported by the 973 Program (No.2013CB933800)National Natural Science Foundation of China (Nos.21525206,21402216,21272243)the Fundamental Research Funds for the Central Universities and Beijing Municipal Commission of Education
文摘We report a turn-on fluorescent probe for H2S through a cascade reaction using a new trap group 4- （bromomethyl）benzoate, based on excited-state intramolecular proton transfer （ESIPT） sensing mechanism. The probe showed good selectivity and high sensitivity towards H2S and it was capable of detecting and imaging H2S in living HeLa cells, indicating its potential biological applications.
基金Financial support from the National Natural Science Foundation of China(Nos. 21472096, J1103306)
文摘A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7：1-20：1 dr under the catalysis of L-diarylprolinol silyl ether. This reaction provides a facile access to highly enantioenriched 4- diphenylphosphinyl chroman-2-ols. It also represents a novel organocatalytic asymmetric phospha- Michael addition of α,β-unsaturated aldehydes with pentavalent P-nucleophiles.
基金supported by the National Natural Science Foundation of China (Nos. 21577037 and 21738002)the State Key Laboratory of Bioreactor Engineering, Shanghai Natural Science Fund (No. 20ZR1414700)+2 种基金Shanghai Sailing Program (No. 19YF1412500)Natural Science Basic Research Program of Shaanxi (No. 2019JQ-924)Key Breeding Program by Collaborative Innovation Center of Green Manufacturing Technology for Traditional Chinese Medicine in Shaanxi Province (No. 2019XT-1-03)。
文摘Selective detection of multiple analytes in a compact design with dual-modality and theranostic features presents great challenges. Herein, we wish to report a coumarin-thiazolidine masked D-penicillamine based dual-modality fluorescent probe COU-DPA-1 for selective detection, differentiation, and detoxification of multiple heavy metal ions(Ag^(+), Hg^(2+), Cu^(2+)). The probe shows divergent fluorescence(FL)/circular dichroism(CD) responses via divergent bond-cleavage cascade reactions(metal ion promoted C-S cleavage and hydrolysis at two distinctive cleavage sites): FL “turn-off” and CD “turn-on” for Ag+(no hydrolysis), FL “turn-on” and CD “turn-off” for Hg^(+)(imine hydrolysis), and FL “self-threshold ratiometric” and CD “turn-off” for excess Cu^(2+)(lactone and imine hydrolysis), providing the first example of a fluorescence/CD dual-modality probe for multiple species with complimentary responses. Moreover, the bond-cleavage cascade reactions also lead to the formation of D-penicillamine heavy metal ion complexes for potential detoxification treatments.
基金supported by Youth Innovation and Technology Project of high School in Shandong Province (No. 2019KJC021)Natural Science Foundation of Qinghai Province of China (No. 2020-ZJ-915)。
文摘A mild and efficient photochemical multi-component tandem reaction of quinoxalin-2(1H)-ones, alkenes and sulfinic acids is reported. This tandem reaction could be conveniently carried out at room temperature by employing 4Cz IPN as the metal-free photocatalyst and dioxygen(air) as the environmentally benign oxidant. A number of sulfonated quinoxalin-2(1H)-ones were obtained in satisfactory yields with favorable functional group tolerance. Radical trapping experiment and fluorescence quenching experiments were performed to elucidate this visible-light mediated radical reaction process.
基金supported by the Research Council of the University of Mazandaran,Iran
文摘A simple synthesis of highly functionalized 2,5-diaminofurans based pyrimidine derivatives from 1-（carboxymethyl）uracil via a multi-component reaction is described. The reactive 1：1 intermediate produced from the reaction of tert-butyl isocyanide and dialkyl acetylenedicarboxylates was trapped at room temperature by 1-（carboxymethyl）uracil derivatives to yield polyfunctio- nalized furan rings in fairly good yields.
基金Project supported by the Young Talent Fund of Association for Science and Technology in Shaanxi(No.20220609)the Natural Science Foundation Research Project of Shaanxi Province(No.2025JC-YBQN-129)+3 种基金the Science and Technology Planning Project of Yan City(No.2022SLSFGG-005)the National College Students'Innovation and Entrepreneurship Training Program(No.202510719063)the Youth Innovation Team Project of Shaanxi Provincial Education Department(No.23JP193)the Youth Innovation Team of Shaanxi Universities。
文摘Organoselenium and pyrazole compounds are important scaffolds in pharmaceutical molecules.Herein,an electrochemical multicomponent one-pot cascade reaction of hydrazide,pentane-2,4-diones and diselenides has been established to construct 4-selenylacylpyrazoles.It is worth noting that for this efficient and green protocol,neither metal catalysts nor external oxidants are required.Moreover,this process exhibits step economy,ease of scale up and high yields to deliver various 4-selenylacylpyrazoles.
基金financial support from Ministry of Science and Technology of China (No.2019ZX09721001-008)National Natural Science Foundation of China (Nos.81773890,22001024,82073997)the “Thousand Talents Program” of Sichuan Province and Xinglin Scholar Research Premotion Project of CDUTCM。
文摘An N-heterocyclic carbene(NHC)-catalysed retro-aldol/aldol cascade reaction of spirooxindole-basedβ-hydroxyaldehyde has been developed.The ring opening-closure process enables the diastereodivergent synthesis of spirocyclopentaneoxindole products with four consecutive stereocenters by simply changing the reaction solvents(THF or DCE).The Michael/aldol/retro-aldol/aldol sequential protocol allows the diastereodivergent synthesis of spirocyclopentaneoxindoles from 3-substituted oxindole andα,β-unsaturated aldehyde under the relay catalysis of a chiral secondary amine and an NHC catalyst.Moreover,four stereoisomers of the product can be selectively provided by using different combinations of a chiral secondary amine and a solvent.
基金supported by National Science Foundation of China(No.20772033)China postdoctoral Science Foundation(No.20080440607)
文摘Oxonium ylide intermediates generated from α-diazocarbonyl compounds and water were trapped by Zn（Ⅱ）-activated α- dicarbonyl compounds. The reaction gave α,β-dihydroxyl acid derivatives in moderate yield.
基金supported by the National Natural Science Foundation of China(Nos.21625205 and U19A2014)。
文摘The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H insertion process.Deuterium labelling experiments,kinetic studies and control experiments were carried out for the rationalization of the mechanism.
基金funded by the National Natural Science Foundation of China(Nos.22271154,M-0411)the China Postdoctoral Science Foundation(No.2023M731658)+2 种基金the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078)the Innovation Support Program of Jiangsu Province(No.BZ2023055)the High-Performance Computing Platform of Peking Uniersity。
文摘Intramolecular end-to-end reactions of long-chain linear precursors remain challenging due to their inherent tendency to undergo intermolecular reactions.Herein,we investigated the cascade hydrolysis and intramolecular cyclization reactions of three vips with varying lengths within the well-defined nanocavities of cavitands in aqueous solution.Driven by hydrophobic effect,these vips were encapsulated within the dimeric capsules,adopting distinct conformations and orientations due to spatial constraints.Specifically,the shorter vip maintained an extended linear geometry,whereas the longer vips adopted a folded binding mode.Upon initiating the reaction,the terminal residue of the shorter vip displayed lower reactivity,while the longer vips,preorganized within the cavity,underwent efficient cyclization,resulting in significant differences in reaction kinetics.Furthermore,electrostatic potential fields played a critical role in modulating reaction rates,with the positively charged cavitand accelerating the reaction more efficiently compared to its negatively charged counterpart,likely due to stabilization of the anionic transition state.This study provides an effective strategy for designing enzymemimetic nanoreactors through the utilization of well-defined nanospaces.
基金supported by Sichuan Science and Technology Program(No.2023NSFSC0101)the 2024 Provincial platform project of Chengdu Normal University(No.GNFZ202404)+1 种基金Natural Science Foundation of Shandong Province(No.ZR2021MB065)National Natural Science Foundation of China(No.22101237)。
文摘A convenient photocatalytic multi-component reaction of alkenes,quinoxalin-2(1H)-ones,and diazo compounds has been developed in the presence of water.A number of ester-containing quinoxalin-2(1H)-ones could be efficiently obtained in moderate to good yields at room temperature.This metal-free visiblelight-driven tandem reaction was conducted through proton-coupled electron transfer(PCET)process using water as the hydrogen donor and 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene(4CzIPN)as the photocatalyst.
基金financially supported by the National Natural Science Foundation of China(No.22207066)Taishan Scholars Program of Shandong Province(No.TS201712065)+2 种基金the Academic Promotion Program of Shandong First Medical University(No.2019QL009)the Science and Technology Funding from Jinan(No.2020GXRC018)the Traditional Chinese Medicine Science and Technology Project of Shandong Province(No.Q-2022142)。
文摘Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research.Herein,through the examination of the catalytic reaction paths of natural nicotinamide adenine dinucleotide(NADH)oxidase(NOX),a novel and efficient single-atom rhodium catalyst(Rh1/NC)was developed to mimic NOX.The Rh_(1)/NC demonstrated the ability to catalyze the dehydrogenation of NADH and transfer electrons to O_(2)to generate H_(2)O_(2)through the typical two-electron pathway.Furthermore,our findings revealed that Rh_(1)/NC exhibits the ability to catalyze the conversion of produced H_(2)O_(2)into OH under mildly acidic conditions.This process amplifies the oxidation of NADH,showcasing NADH peroxidase-like activity(NPx-like).As a paradigm,this unique dual enzyme-like property of Rh_(1)/NC with a positive feedback effect holds significance in disrupting cancer cellular homeostasis.Rh_(1)/NC can effectively consume NADH via cascade biocatalytic reactions within cancer cells,further triggering the elevation of reactive oxygen species(ROS),leading to impaired oxidative phosphorylation and decreased mitochondrial membrane potential,thus damaging the adenosine triphosphate(ATP)synthesis.The resulting'domino effect'interferes with the energy metabolism homeostasis of cancer cells,ultimately promoting cell apoptosis.This study provides potential guidance for the rational design of materials with greater capabilities.
