A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-...A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.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
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the...The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.展开更多
An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substi...An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.展开更多
One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and ...One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and optimal ranges of the number of machines that can be used in a cascade?For the first time,the permissible and optimal ranges of the number of gas centrifuges that can be utilized in a cascade were investigated using two types of centrifuges,and the performance of small and large tapered cascades was discussed.The particle swarm optimization algorithm(PSO)has been used to optimize tapered cascades.The results show:(1)For the first centrifuge,41 cascades(91≤n≤4897)and for the second centrifuge,49 cascades(18≤n≤3839)with small and large sizes can be used in enrichment facilities,and the best cascade for them has 530(with 23 stages)and 39(with 7 stages)centrifuges,respectively.(2)For both centrifuges,when 600≤n(number of centrifuges=n),the large cascade performance changes are relatively insignificant.(3)For both types of gas centrifuges,the annual los s of separation power in enrichment facilities is approximately 1.25%-4.82%of the total separation work required.展开更多
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation inv...Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.展开更多
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report ph...Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.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
By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-fr...By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-friendly bis(methoxypropy)ether under metal-,hazardous additive-,photocatalyst-free conditions was established.展开更多
A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excel...A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.展开更多
A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three conti...A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.展开更多
We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-...We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives.With the TBAI–TBHP catalytic system,a broad series of structurally diverse indolo[2,1-a]isoquinolin-6(5H)-one derivatives were obtained in moderate to excellent yields.The reaction features mild reaction conditions,operationally easiness,scaled-up feasibility,and high functional-group-tolerance.展开更多
A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], ...A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], using DBU as an efficient catalyst and ethylene glycol as an environmentally benign solvent. More diverse 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] analog libraries were prepared in good yields（up to 97%）. The structure of 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] was confirmed by mass spectrometry analysis, NMR analysis and single crystal X-ray diffraction. The main advantages of this method include the availability of starting materials, simple experimental operation, short reaction time,as well as high yields observed.展开更多
A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,...A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.展开更多
An efficient method for the synthesis of functionalized chroman-4-ones induced by visible light via the radical cyclization reaction of sulfinic acids and o-(allyloxy)arylaldehydes at room temperature was described.Th...An efficient method for the synthesis of functionalized chroman-4-ones induced by visible light via the radical cyclization reaction of sulfinic acids and o-(allyloxy)arylaldehydes at room temperature was described.The corresponding products were isolated with moderate to good yields.Radical mechanism was proposed fo r this trans formation.Anti-microbial activity of some desired compounds we re screened.展开更多
Gastric carcinoma(GC)is a malignancy with multifactorial involvement,multicellular regulation,and multistage evolution.The classic Correa's cascade of intestinal GC specifies a trilogy of malignant transformation ...Gastric carcinoma(GC)is a malignancy with multifactorial involvement,multicellular regulation,and multistage evolution.The classic Correa's cascade of intestinal GC specifies a trilogy of malignant transformation of the gastric mucosa,in which normal gastric mucosa gradually progresses from inactive or chronic active gastritis(Phase I)to gastric precancerous lesions(Phase II)and finally to GC(Phase III).Correa's cascade highlights the evolutionary pattern of GC and the importance of early intervention to prevent malignant transformation of the gastric mucosa.Intervening in early gastric mucosal lesions,i.e.,Phases I and II,will be the key strategy to prevent and treat GC.Natural products(NPs)have been an important source for drug development due to abundant sources,tremendous safety,and multiple pharmacodynamic mechanisms.This review is the first to investigate and summarize the multi-step effects and regulatory mechanisms of NPs on the Correa's cascade in gastric carcinogenesis.In Phase I,NPs modulate Helicobacter pylori urease activity,motility,adhesion,virulence factors,and drug resistance,thereby inhibiting H.pylori-induced gastric mucosal inflammation and oxidative stress,and facilitating ulcer healing.In Phase II,NPs modulate multiple pathways and mediators regulating gastric mucosal cell cycle,apoptosis,autophagy,and angiogenesis to reverse gastric precancerous lesions.In Phase III,NPs suppress cell proliferation,migration,invasion,angiogenesis,and cancer stem cells,induce apoptosis and autophagy,and enhance chemotherapeutic drug sensitivity for the treatment of GC.In contrast to existing work,we hope to uncover NPs with sequential therapeutic effects on multiple phases of GC development,providing new ideas for gastric cancer prevention,treatment,and drug development.展开更多
Broad area quantum cascade lasers(BA QCLs)have significant applications in many areas,but suffer from demanding pulse operating conditions and poor beam quality due to heat accumulation and generation of high order mo...Broad area quantum cascade lasers(BA QCLs)have significant applications in many areas,but suffer from demanding pulse operating conditions and poor beam quality due to heat accumulation and generation of high order modes.A structure of mini-array is adopted to improve the heat dissipation capacity and beam quality of BA QCLs.The active region is etched to form a multi-emitter and the channels are filled with In P:Fe,which acts as a lateral heat dissipation channel to improve the lateral heat dissipation efficiency.A device withλ~4.8μm,a peak output power of 122 W at 1.2%duty cycle with a pulse of 1.5μs is obtained in room temperature,with far-field single-lobed distribution.This result allows BA QCLs to obtain high peak power at wider pump pulse widths and higher duty cycle conditions,promotes the application of the mid-infrared laser operating in pulsed mode in th e field of standoff photoacoustic chemical detection,space optical communication,and so on.展开更多
基金funds from Natural Science Foundation of Guangxi Province(Nos.2023GXNSFBA026304,2023GXNSFDA026063)the Guangxi Science and Technology Base and Special Talents(No.Guike AD20159047).
文摘A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.
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financial support from the National Natural Science Foundation of China(Nos.22125108,22101238,22331004 and 22121001)Yunnan Fundamental Research Project(No.202401CF070024)+2 种基金Natural Science Foundation of Jiangsu Province(No.BK20211059)the Project of Science and Technology of Xuzhou Government(No.KC22080)NFFTBS(No.J1310024)。
文摘The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis.However,examples of asymmetric Meinwald rearrangements are quite scarce,and these reactions have so far been limited to the use of chiral Br?nsted acids as catalysts.Here,we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction,allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities.Thus,this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement,but also constitutes the first example of asymmetric formal monocarbon insertion into C-O bond of ester.Moreover,theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
基金the Scientific Research Fund of Hunan Provincial Education Department(21B0262 and 22B1094)the Natural Science Foundation of Hunan Province(2022JJ40857)the Hunan Provincial Innovation Foundation For Postgraduate(CX20230757)forfinancial support.
文摘An alkyl radical initiated cyclization/tandem reaction of alkyl bromides and alkyl electrophiles by using potassium metabisulphite(K_(2)S_(2)O_(5))as a connector is developed for the synthesis of various lactam-substituted alkyl sulfones.Notably,this process does not require a metal catalyst or metal powder reductant,highlighting its environmentally friendly features.The reaction demonstrates outstanding substrate adaptability and a high tolerance towards diverse functional groups.Furthermore,the biologically active molecules and commercially available drugs with a late-stage modification are also highly compatible with this transformation.Mechanistic studies revealed that the reaction proceeds through a single-step process involving intramolecular radical cyclization,"SO_(2)"insertion,and external alkyl incorporation.
文摘One of the main issues in designing optimum tapered cascades for uranium enrichment for annual fuel production in a power reactor is whether to employ large(fat)or small(thin)cascades.What will be the permissible and optimal ranges of the number of machines that can be used in a cascade?For the first time,the permissible and optimal ranges of the number of gas centrifuges that can be utilized in a cascade were investigated using two types of centrifuges,and the performance of small and large tapered cascades was discussed.The particle swarm optimization algorithm(PSO)has been used to optimize tapered cascades.The results show:(1)For the first centrifuge,41 cascades(91≤n≤4897)and for the second centrifuge,49 cascades(18≤n≤3839)with small and large sizes can be used in enrichment facilities,and the best cascade for them has 530(with 23 stages)and 39(with 7 stages)centrifuges,respectively.(2)For both centrifuges,when 600≤n(number of centrifuges=n),the large cascade performance changes are relatively insignificant.(3)For both types of gas centrifuges,the annual los s of separation power in enrichment facilities is approximately 1.25%-4.82%of the total separation work required.
基金financially supported by grants from the National Key Research and Development Program of China (No.2024YFE0102000)the National Natural Science Foundation of China (Nos.81925037,82321004,U22A20371,U24A20782,32170060,22177037,22207039,22307045)+6 种基金the Guangdong Major Project of Basic and Applied Basic Research (No.2023B0303000026)the Guangdong Natural Science Funds for Distinguished Young Scholars (No.2022B1515020028,China)the Guangdong International Science and Technology Cooperation Base (No.2021A0505020015,China)the Guangdong Basic and Applied Basic Research Foundation (Nos.2023B1515040016,2023A1515110388)the Innovative and Research Teams Project of Guangdong Higher Education Institution (No.2021KCXTD001,China)the Guangzhou Science and Technology Project (Nos.202206010020,2024A04J6241,2023A04J0080,China)the Fundamental Research Funds for the Central Universities (Nos.21623105,21624210)。
文摘Mangicol-type sesterterpenoids possess potent anti-inflammatory activity,characterized by a 5-5-6-5tetracyclic carbon skeleton formed by mangicdiene synthase Fg MS.Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization(path a) or C2-C10 cyclization(path b) after the C10carbocation formation,but neither has been experimentally validated.Here,we have identified a second mangicdiene synthase Man D,which is derived from Fusarium sp.JNU-XJ070152-01 and shares high amino acid sequence identity with Fg MS.Through heterologous expression of man D in Aspergillus oryzae NSAR1,we observed production not only of mangicdiene(1) and variecoltetraene(2),previously identified by expression of Fg MS in Escherichia coli,but also two novel sesterterpene skeletons fusadiene(3)and fusatriene(4).The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b,thus experimentally confirming that mangicdiene is built via path b for the first time,consistent with previous density functional theory(DFT) calculation results.
基金National Natural Science Foundation of China (NSFC) (No.22131008)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials.Herein,we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission,which is constructed by cucurbit[7]uril(CB[7]),cyanostilbene derivative(DAC)and Laponite XLG(LP)via supramolecular cascade assembly.Compared with the free vip molecule DAC,the confinement of macrocycle CB[7]achieve effective near-infrared fluorescence in the aqueous phase from scratch,and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC,which not only result in a substantial enhancement of the fluorescence intensity,but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states.Further,8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt(HPTS)is introduced in the cascade assembly to fabricated photocontrollable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer,which is successfully employed in reversible multiple information encryption.
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the Hunan Provincial Natural Science Foundation of China(No.2019JJ20008)。
文摘By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-friendly bis(methoxypropy)ether under metal-,hazardous additive-,photocatalyst-free conditions was established.
文摘A novel type of palladium-catalyzed cascade cyclization-coupling reaction has been found. Reaction of N, N-diallylbenzoylamide 1 with benzyl halides 2 afforded the corresponding dihydropyrroles 3 in moderate to excellent yields.
基金supported by the Natural Science Foundation of China(Nos.21871293 and 22071264)。
文摘A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.
基金the State Key Basic Research Program of the People’s Republic of China (No. 2018YFC0310900)National Natural Science Foundation of China (Nos. 21871018, 21801005, 21732001)+7 种基金Shenzhen Science and Technology Innovation Committee (Nos. KQTD20190929174023858, JCYJ20180504165454447)Industry and Information Technology Bureau of Shenzhen Municipality (No. 201806151622209330)Guangdong Science and Technology Program (No. 2017B030314002)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions (No. 2019SHIBS0004)the National Ten Thousand Talent Program (the Leading Talent Tier) for the financial supportthe Science and Technology Project of Henan Province (No. 202102310328)the Henan Postdoctoral Foundationthe Postdoctoral Innovation Base of Anyang Institute of Technology for financial support
文摘We have developed a metal-free radical cascade reaction of N-substituted 2-aryl indoles with readily available sulfonyl hydrazides for the rapid construction of arylsulfonyl-substituted indolo[2,1-a]isoquinolin-6(5H)-one derivatives.With the TBAI–TBHP catalytic system,a broad series of structurally diverse indolo[2,1-a]isoquinolin-6(5H)-one derivatives were obtained in moderate to excellent yields.The reaction features mild reaction conditions,operationally easiness,scaled-up feasibility,and high functional-group-tolerance.
基金Financial support for this work by the National Natural Science Foundation of China(No.81202403)West China HospitalChengdu Science and Technology Department Translational Medicine Innovation Foundation(No.ZH13039)
文摘A simple and efficient cascade Michael/cyclization reaction of 3-aminoindolin-2-ones with enones/enals was identified for the synthesis of potentially biologically active 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles], using DBU as an efficient catalyst and ethylene glycol as an environmentally benign solvent. More diverse 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] analog libraries were prepared in good yields（up to 97%）. The structure of 3＇,4＇-dihydrospiro[pyrrol-3,2＇-oxindoles] was confirmed by mass spectrometry analysis, NMR analysis and single crystal X-ray diffraction. The main advantages of this method include the availability of starting materials, simple experimental operation, short reaction time,as well as high yields observed.
基金financial support from the National Natural Science Foundation of China(No.22171215)the Excellent Youth Foundation of Hubei Scientific Committee(No.2022CFA092)the GuangDong Basic and Applied Basic Research Foundation(No.2022A1515110113).
文摘A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.
基金the National Natural Science Foundation of China(No.21772107)Shandong Province Key Research and Development Plan(No.2019GSF108017)。
文摘An efficient method for the synthesis of functionalized chroman-4-ones induced by visible light via the radical cyclization reaction of sulfinic acids and o-(allyloxy)arylaldehydes at room temperature was described.The corresponding products were isolated with moderate to good yields.Radical mechanism was proposed fo r this trans formation.Anti-microbial activity of some desired compounds we re screened.
基金supported by the Chengdu University of Traditional Chinese Medicine"Xinglin Scholars"Program,China(Grant No.:MPRC2023014).
文摘Gastric carcinoma(GC)is a malignancy with multifactorial involvement,multicellular regulation,and multistage evolution.The classic Correa's cascade of intestinal GC specifies a trilogy of malignant transformation of the gastric mucosa,in which normal gastric mucosa gradually progresses from inactive or chronic active gastritis(Phase I)to gastric precancerous lesions(Phase II)and finally to GC(Phase III).Correa's cascade highlights the evolutionary pattern of GC and the importance of early intervention to prevent malignant transformation of the gastric mucosa.Intervening in early gastric mucosal lesions,i.e.,Phases I and II,will be the key strategy to prevent and treat GC.Natural products(NPs)have been an important source for drug development due to abundant sources,tremendous safety,and multiple pharmacodynamic mechanisms.This review is the first to investigate and summarize the multi-step effects and regulatory mechanisms of NPs on the Correa's cascade in gastric carcinogenesis.In Phase I,NPs modulate Helicobacter pylori urease activity,motility,adhesion,virulence factors,and drug resistance,thereby inhibiting H.pylori-induced gastric mucosal inflammation and oxidative stress,and facilitating ulcer healing.In Phase II,NPs modulate multiple pathways and mediators regulating gastric mucosal cell cycle,apoptosis,autophagy,and angiogenesis to reverse gastric precancerous lesions.In Phase III,NPs suppress cell proliferation,migration,invasion,angiogenesis,and cancer stem cells,induce apoptosis and autophagy,and enhance chemotherapeutic drug sensitivity for the treatment of GC.In contrast to existing work,we hope to uncover NPs with sequential therapeutic effects on multiple phases of GC development,providing new ideas for gastric cancer prevention,treatment,and drug development.
文摘Broad area quantum cascade lasers(BA QCLs)have significant applications in many areas,but suffer from demanding pulse operating conditions and poor beam quality due to heat accumulation and generation of high order modes.A structure of mini-array is adopted to improve the heat dissipation capacity and beam quality of BA QCLs.The active region is etched to form a multi-emitter and the channels are filled with In P:Fe,which acts as a lateral heat dissipation channel to improve the lateral heat dissipation efficiency.A device withλ~4.8μm,a peak output power of 122 W at 1.2%duty cycle with a pulse of 1.5μs is obtained in room temperature,with far-field single-lobed distribution.This result allows BA QCLs to obtain high peak power at wider pump pulse widths and higher duty cycle conditions,promotes the application of the mid-infrared laser operating in pulsed mode in th e field of standoff photoacoustic chemical detection,space optical communication,and so on.
