An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist o...An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist of inexpensive rose bengal as photocatalyst to prepare a series of alkyl substituted oxazolines in moderate to excellent yields. High regioselectivity, operational safety, mild conditions and excellent substrate generality give this protocol broad application prospects.展开更多
A practical,metal-,and additive-free strategy for photo-and electro-induced perfluoroalkylation/cyclization of ohydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed.Var...A practical,metal-,and additive-free strategy for photo-and electro-induced perfluoroalkylation/cyclization of ohydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed.Various fluoroalkyl chromones were efficiently assembled in moderate to good yields.The scalability of this protocol and the assembling of diverse nitrogen-containing heterocycles from late-stage transformations of fluoroalkyl chromones greatly broaden the practical applications of this developed protocol.展开更多
Lignin-derived oxygenated aromatics,particularly phenols and aromatic ethers obtained through depolymerization,represent promising feedstocks for synthesizing high-density and high-heat-sink aviation fuels via alkylat...Lignin-derived oxygenated aromatics,particularly phenols and aromatic ethers obtained through depolymerization,represent promising feedstocks for synthesizing high-density and high-heat-sink aviation fuels via alkylation-hydrogenation processes.This study systematically evaluates the catalytic performance of various zeolites(Hβ,HZSM-5,MCM-41 and HUSY)in the alkylation reaction of phenol with cyclohexanol.Characterization results demonstrate that HUSY zeolite showed superior catalytic activity compared to other zeolites,attributable to its favorable pore architecture and well-balanced acid site distribution that synergistically facilitate molecular diffusion and catalytic transformations.To further enhance the catalytic properties,HUSY zeolite was modified with citric acid at various concentrations and compared with those treated with NaOH and oxalic acid.The results revealed that citric acid treatment preserved the crystallinity of the zeolite while modulating its acid distribution and pore structure.All modified zeolites enhanced phenol alkylation activity.Notably,the HUSY-0.5M catalyst,which exhibited the highest medium-strong acid to total acid ratio,achieved superior catalytic performance,80.4%conversion of phenol and 99.6%selectivity for alkylation products.The catalyst also exhibited high activity in the alkylation of various lignin-derived compounds,demonstrating its broad applicability.This work provides a new strategy for the valorization of lignin-derived phenols into high-value fuel precursors through alkylation.展开更多
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
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
A photocatalyst-and metal-free radical tandem alkylation/cyclization between 1,6-dienes and redox-active esters has been devel-oped,affording a series of N-aryl pyrrolidine-2-ones in moderate to good yields.The transf...A photocatalyst-and metal-free radical tandem alkylation/cyclization between 1,6-dienes and redox-active esters has been devel-oped,affording a series of N-aryl pyrrolidine-2-ones in moderate to good yields.The transformation is driven by the formation of an electron-donor-acceptor(EDA)complex and a subsequent single electron transfer(SET)process.This photocatalyst-free protocol features excellent regioselectivity,mild conditions and broad substrate scope,providing a facile access to 3-alkyl-3,4-dimethyl-1-phe-nylpyrrolidin-2-one.展开更多
A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been...A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been developed.This approach utilizes lithium iodide(LiI)and triphenylphosphine(PPh_(3))as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor-acceptor(EDA)complex.A series of primary,secondary,and tertiary alkyl-substituted phenanthridines are prepared in up to 82%yield without transition-metal catalysts,chemical oxidants,or metal-/organic dye-based photocatalysts.展开更多
The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Insp...The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Be...Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.展开更多
Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]iso...Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]isoquinolin-6(5H)-one derivatives using the inexpensive and easy-to-handle HCF_(2)SO_(2)Na as an HCF2 sources.Diverse difluoromethylated indolo[2,1-a]isoquinolines were readily obtained in moderate to good yields.Mechanistic studies demonstrate that the reaction may involve a radical process.展开更多
Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of...Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.展开更多
N-(2-Ethynylphenyl)acrylamides have emerged as key intermediates for the synthesis of complex heteropolycyclic compounds.The recent advances focus on the tandem cyclization involving these precursors,among which forma...N-(2-Ethynylphenyl)acrylamides have emerged as key intermediates for the synthesis of complex heteropolycyclic compounds.The recent advances focus on the tandem cyclization involving these precursors,among which formation of fused six/N-three,six/five(N,S,O),and six/six-membered rings are highlighted.Nitrogen,sulfur,and oxygen incorporations into five-membered rings provide efficient routes to bioactive polycyclic molecules.These cyclization reactions exhibit excellent atom economy,high efficiency,and good functional group compatibility.Furthermore,novel catalytic systems and photochemical strategies also expand the synthetic applications of these precursors.Taken together,these advancements offer versatile tools for the synthesis of intricate heterocyclic scaffolds with broad applications in organic and medicinal chemistry.展开更多
Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkyl...Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.展开更多
Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the con...Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.展开更多
The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-h...The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.展开更多
The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeo...The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeolites is well maintained.However,it's found that these Ce^(3+)species can produce the Bronsted acid sites by the dissociation of water molecules owing to the electrostatic field of Ce^(3+)cations,the splitting of water molecules occurs following[Ce(H_2O)_n]^(3+)■Ce[(OH)(H_2O)_(n-1)]^(2+)+H^(+)equation based on the Plank-Hirschler mechanism,leading to superior activity of resultant cerium-silicate pillared MWW zeolites in the alkylation between benzene with 1-dodecene.Moreover,the additional Ce species located in the silica pillars can be easily accessed by vip molecules due to the presence of mesopores between neighboring MWW layers,which can strongly active benzene molecules by polarization effect,and dodecyl carbenium ions are preferred to attack the carbon atoms located in activated benzene molecules,resulting in the long lifetime of cerium-silicate pillared MWW zeolites since the oligomerization of long-chain olefins is suppressed.Under harsh reaction conditions(benzene/1-dodecene=10,WHSV=20 h^(-1)),the optimized cerium-silicate pillared MWW zeolite shows outstanding activity(>40%)and excellent selectivity(>85%)of 2-LAB in the alkylation of benzene with 1-dodecene.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
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
Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficientl...Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficiently accomplished from the key intermediate(S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP.(S)-6,bearing three contiguous chiral centers,was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen,which was less developed,primarily due to the incompatibility of basic nitrogen under acidic reaction conditions.This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously.Furthermore,the mechanism of the Nazarov cyclization and the origin of the regio-and diastereoselectivity were elucidated by DFT calculations and deuteration experiments,providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.展开更多
基金supported by the National Natural Science Foundation of China (No. 22078299)Zhejiang Provincial Natural Science Foundation of China (Nos. LY21B060005, LQ20B060007)+1 种基金the College of Pharmaceutical Sciences, Zhejiang University of TechnologyCollaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals for the financial help。
文摘An efficient photocatalytic alkylation/cyclization of allylic amide with N-hydroxyphthalimide ester has been developed. The transformation is taken advantage of alkyl radicals to attack allylic amide with the assist of inexpensive rose bengal as photocatalyst to prepare a series of alkyl substituted oxazolines in moderate to excellent yields. High regioselectivity, operational safety, mild conditions and excellent substrate generality give this protocol broad application prospects.
基金the National Natural Science Foundation of China(No.22178314 and 21776254)the Zhejiang Provincial Key R&D Project(No.2021C03148)the Opening Project of Zhejiang Engineering Research Center of Fat-soluble Vitamin(2023)for financial help(No.202306).
文摘A practical,metal-,and additive-free strategy for photo-and electro-induced perfluoroalkylation/cyclization of ohydroxyaryl enaminones with sodium perfluoroalkanesulfinates under mild conditions has been developed.Various fluoroalkyl chromones were efficiently assembled in moderate to good yields.The scalability of this protocol and the assembling of diverse nitrogen-containing heterocycles from late-stage transformations of fluoroalkyl chromones greatly broaden the practical applications of this developed protocol.
基金Supported by National Key Research&Development Program of China (2022YFB4201800)Key Program of National Natural Science Foundation of China (52130610)。
文摘Lignin-derived oxygenated aromatics,particularly phenols and aromatic ethers obtained through depolymerization,represent promising feedstocks for synthesizing high-density and high-heat-sink aviation fuels via alkylation-hydrogenation processes.This study systematically evaluates the catalytic performance of various zeolites(Hβ,HZSM-5,MCM-41 and HUSY)in the alkylation reaction of phenol with cyclohexanol.Characterization results demonstrate that HUSY zeolite showed superior catalytic activity compared to other zeolites,attributable to its favorable pore architecture and well-balanced acid site distribution that synergistically facilitate molecular diffusion and catalytic transformations.To further enhance the catalytic properties,HUSY zeolite was modified with citric acid at various concentrations and compared with those treated with NaOH and oxalic acid.The results revealed that citric acid treatment preserved the crystallinity of the zeolite while modulating its acid distribution and pore structure.All modified zeolites enhanced phenol alkylation activity.Notably,the HUSY-0.5M catalyst,which exhibited the highest medium-strong acid to total acid ratio,achieved superior catalytic performance,80.4%conversion of phenol and 99.6%selectivity for alkylation products.The catalyst also exhibited high activity in the alkylation of various lignin-derived compounds,demonstrating its broad applicability.This work provides a new strategy for the valorization of lignin-derived phenols into high-value fuel precursors through alkylation.
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supported by the National Natural Science Foundation of China(22078299 and 22108250)the Natural Science Foundation,of Zhejiang Province(LY21B060005 and LQ20B06007)Research project of Zhejiang Provincial Department of Education(Y20840109)。
文摘A photocatalyst-and metal-free radical tandem alkylation/cyclization between 1,6-dienes and redox-active esters has been devel-oped,affording a series of N-aryl pyrrolidine-2-ones in moderate to good yields.The transformation is driven by the formation of an electron-donor-acceptor(EDA)complex and a subsequent single electron transfer(SET)process.This photocatalyst-free protocol features excellent regioselectivity,mild conditions and broad substrate scope,providing a facile access to 3-alkyl-3,4-dimethyl-1-phe-nylpyrrolidin-2-one.
基金supported by the National Natural Science Foundation of China(22078084)the Scientific Research Fund of Hunan Provincial Education Department(22B0674)the Science and Natural Science Foundation of Hunan Province(Nos.2023J30273 and 2023J40301).
文摘A visible-light-induced decarboxylative radical cascade cyclization reaction between N-(2-cyanoaryl)-acrylamides and alkyl N-(acyloxy)phthalimide(NHPI esters)for the construction of phenanthridine derivatives has been developed.This approach utilizes lithium iodide(LiI)and triphenylphosphine(PPh_(3))as the redox catalysts and the alkyl radical is produced through the photoactivation of the electron donor-acceptor(EDA)complex.A series of primary,secondary,and tertiary alkyl-substituted phenanthridines are prepared in up to 82%yield without transition-metal catalysts,chemical oxidants,or metal-/organic dye-based photocatalysts.
基金the"100 Talent Program of Chinese Academy of Sciences""1000-Youth Talents Plan"+3 种基金ShanghaiYouth Talent,National Science&Technology Major Project"Key New Drug Creation and Manufacturing Program"China(No. 2018ZX09711002–006)Science and Technology Commission of Shanghai Municipality (No. 18431907100)ShanghaiTechnology Innovation Action Plan (No. 18JC1415300)the Research Grants Council of Hong Kong (No. HKUST 16302418) for financial support of this research。
文摘The development of innovative strategies and methods to provide natural product-like macrocycles not accessible by biosynthesis, but endowed with novel bioactivities and simplified structure, is highly desirable. Inspired by the key scaffolds of rapamycin and FR252921, herein, we report a Rh(III)-catalyzed C–H alkylation macrocyclization, which enables access to CF_(3)-substituted macrolides. DFT calculations reveal that the chemoselectivity between C–H alkylation and olefination macrocyclization was highly controllable. Moreover, the unique CF_(3)-substituted macrolides showed potent anti-inflammation activities against TNF-α, IL-6 and CCL2 m RNA expression.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.20874026 and 91023008)Ph.D.Programs Foundation of Ministry of Education of China(20100074110002)+1 种基金the Fundamental Research Funds for the Central Universities,Shanghai Leading Academic Discipline Project(B502)AH thanks the"Eastern Scholar Professorship"support from Shanghai local government
文摘Several new enediynes with long chain alkyl groups were synthesized through Sonogashira coupling reactions between long chain alkynes and（Z）-1,2-dichloroethene. These enediynes（1） were then subjected to thermal Bergman cyclization in a refluxing diphenyl ether bath under vacuum to obtain conjugated polyphenylenes with the weight-average molecular weights up to 4.9 × 103 g·mol·1. The occurrence of Bergman cyclization was confirmed by 1H-NMR, 13C-NMR, and IR spectroscopic analysis. These polyphenylenes are fully soluble in common organic solvents and exhibit good thermal stability. The optical properties of the polyphenylenes were investigated by UV-Vis absorption and photoluminescence（PL） spectroscopies. A blue emission was observed for all these polyphenylenes.
文摘Difluoromethyl compounds are widely found in natural products,bioactive molecule and pharmaceuticals.A visible-light induced difluoromethylation/cyclization of 2-aryl indoles is described to construct indolo[2,1-a]isoquinolin-6(5H)-one derivatives using the inexpensive and easy-to-handle HCF_(2)SO_(2)Na as an HCF2 sources.Diverse difluoromethylated indolo[2,1-a]isoquinolines were readily obtained in moderate to good yields.Mechanistic studies demonstrate that the reaction may involve a radical process.
文摘Polyfluoroarenes represent an essential group of compounds in the fields of medical and material chemistry.It is still a challenge to synthesize alkylated polyfluoroarenes.Herein,a Ni-catalyzed reductive alkylation of polyfluoroarenes with alkyl halides under mild conditions is reported.Polyfluoroarenes(3~6 F)can reacted smoothly with a diverse range of alkyl halides,such as primary,secondary,and tertiary alkyl iodides.The efficient formation of C(sp2)—C(sp3)can be achieved through the combination of Ni catalysis and(Bpin)2/K2CO3 as terminal reductant.
基金Project supported by the Special Fund Project for Scientific Research Openness of the Key Laboratory of Medical Conditioning Functional Food Processing Technology in Weihai City(No.WHYY20240006)the Mid-Young Teachers Visiting Program of Qingdao Agricultural University(No.2024)+1 种基金the General Education Reform and Research Project of Qingdao Agricultural University(No.XJY2024063)the Research Results of the Ideological and Political Education Research Project of Qingdao Agricultural University(No:QNSZ2025023)。
文摘N-(2-Ethynylphenyl)acrylamides have emerged as key intermediates for the synthesis of complex heteropolycyclic compounds.The recent advances focus on the tandem cyclization involving these precursors,among which formation of fused six/N-three,six/five(N,S,O),and six/six-membered rings are highlighted.Nitrogen,sulfur,and oxygen incorporations into five-membered rings provide efficient routes to bioactive polycyclic molecules.These cyclization reactions exhibit excellent atom economy,high efficiency,and good functional group compatibility.Furthermore,novel catalytic systems and photochemical strategies also expand the synthetic applications of these precursors.Taken together,these advancements offer versatile tools for the synthesis of intricate heterocyclic scaffolds with broad applications in organic and medicinal chemistry.
文摘Direct enantioselective allylic C—H functionalization has emerged as a powerful strategy for the asymmetric syn-thesis of highly valuable chiral products.Herein,a Rh(III)-catalyzed enantioselective allylic C—H alkylation of unactivated alkenes withα-diazo carbonyl compounds is described,enabling direct access to chiral products with high efficiency(up to 77%yield,92%ee,and>10∶1 B/L(branched/linear)selectivity).This atom-and step-economical protocol directly converts simple,unactivated substrates into valuable enantioenriched products under mild conditions,providing an efficient catalytic system for asymmetric allylic C—H functionalization.
文摘Indole[2,1-α]isoquinolines are an important class of bioactive molecules and show good antibacterial activity.In the present study,an efficient copper(I)-catalyzed acylation/cyclization has been developed for the construction of indolo[2,1-α]isoquinoline derivatives by utilizing 2-aryl-N-acryloyl indole and benzohydrazide as reactants in the presence of CuI as catalyst and tert-butyl hydroperoxide as oxidant.The present protocol exhibits good functional group tolerance,and a series of acylated indole[2,1-α]isoquinolines were synthesized in moderate to good yields.Radical trapping experiments indicated that the reaction may involve a radical process.
基金financially supported by the Ministry of Science and Technology of China(No.2017YFA0204902)the National Natural Science Foundation of China(Nos.21901217,22101241)。
文摘The controlled incorporation of heptagons into helicene frameworks offers a promising approach to modulate their structural and electronic properties.This study demonstrates the synthesis of two heptagonembedded oxa-helicenes:one with a single heptagon(5)and another with two heptagons(6),achieved through controlled oxidative cyclization of a triple oxa-helicene(4).UV-vis absorption and emission spectra revealed red-shifts and slight increases in Stokes shifts from 4 to 6,attributed toπ-system extension and greater structural relaxation in the excited state.5 and 6 exhibited fluorescence quantum yields 2-3times higher than 4.Chiral separation and thermal stability analyses showed a significant decrease in enantiomeric stability for 5 and 6 compared to 4,due to planarization effects induced by heptagon incorporation.The chiroptical properties were also investigated,revealing reduced optical dissymmetry factors after heptagon embedding.
基金supported by the National Natural Science Foundation of China(22278090,21978055)Natural Science Foundation of Guangdong Province,China(2022A1515012088)。
文摘The cerium-silicate pillared MWW zeolites are fabricated by introducing Ce species into the silica pillars within adjacent MWW layers through a liquid-phase pillaring method,and the multiple-layer structure of MWW zeolites is well maintained.However,it's found that these Ce^(3+)species can produce the Bronsted acid sites by the dissociation of water molecules owing to the electrostatic field of Ce^(3+)cations,the splitting of water molecules occurs following[Ce(H_2O)_n]^(3+)■Ce[(OH)(H_2O)_(n-1)]^(2+)+H^(+)equation based on the Plank-Hirschler mechanism,leading to superior activity of resultant cerium-silicate pillared MWW zeolites in the alkylation between benzene with 1-dodecene.Moreover,the additional Ce species located in the silica pillars can be easily accessed by vip molecules due to the presence of mesopores between neighboring MWW layers,which can strongly active benzene molecules by polarization effect,and dodecyl carbenium ions are preferred to attack the carbon atoms located in activated benzene molecules,resulting in the long lifetime of cerium-silicate pillared MWW zeolites since the oligomerization of long-chain olefins is suppressed.Under harsh reaction conditions(benzene/1-dodecene=10,WHSV=20 h^(-1)),the optimized cerium-silicate pillared MWW zeolite shows outstanding activity(>40%)and excellent selectivity(>85%)of 2-LAB in the alkylation of benzene with 1-dodecene.
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 the National Natural Science Foundation of China(Nos.81725021,81903461)the National Key R&D Program of China(No.2022YFA1503200)the Natural Science Foundation of Hubei Province(No.ZRMS2023000340)。
文摘Asperfilasin A(1),featuring a unique 5/5 cyclopenta[c]pyrrol-one bicyclic core,represents a newly discovered skeletal cytochalasan isolated from Aspergillus flavipes.The enantioselective total synthesis was efficiently accomplished from the key intermediate(S)-6 with three contiguous stereocenters in 5 steps and the synthetic 1 induced G2/M-phase cell cycle arrest of HT29 cells and apoptosis of HL60 and NB4 cells by activation of caspase-3 and degradation of PARP.(S)-6,bearing three contiguous chiral centers,was efficiently constructed by a novel Nazarov cyclization reaction containing basic nitrogen,which was less developed,primarily due to the incompatibility of basic nitrogen under acidic reaction conditions.This reaction allows a wide range of pentadienone substrates containing basic nitrogen to undergo Nazarov cyclization in a single regioselective and diastereoselective manner and is capable of generating three stereocenters simultaneously.Furthermore,the mechanism of the Nazarov cyclization and the origin of the regio-and diastereoselectivity were elucidated by DFT calculations and deuteration experiments,providing valuable insights into the reaction and serving as a guide for future applications involving substrates containing basic nitrogen.
