Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key ...Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key intermediate 18 for the chiral synthesis of 2 and 3 was prepared from new chiral sulfone 7 by the same method.展开更多
One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.
Arenesulfonyl chloride undergoes a facile one-pot coupling reaction with active halides assisted by zinc to give the corresponding sulfones in acceptable yields.
The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically af...(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.展开更多
Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations...Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,σ+^2 andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.展开更多
β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid...β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.展开更多
A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important priv...A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.展开更多
As an attractive C1 synthon,carbon dioxide(CO_(2))has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones ...As an attractive C1 synthon,carbon dioxide(CO_(2))has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones has been developed under transition-metal-free conditions.All the cinnamic acids and the derivatives are obtained selectively in the E-configuration.Besides,arylpropiolates also can be produced from alkynyl sulfones.展开更多
The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ethe...The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.展开更多
Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framewo...Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.展开更多
The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Never...The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.展开更多
Wheat germplasm is a fundamental resource for basic research,applied studies,and wheat breeding,which can be enriched normally by several paths,such as collecting natural lines,accumulating breeding lines,and introduc...Wheat germplasm is a fundamental resource for basic research,applied studies,and wheat breeding,which can be enriched normally by several paths,such as collecting natural lines,accumulating breeding lines,and introducing mutagenesis materials.Ethyl methane sulfonate(EMS)is an alkylating agent that can effectively introduce genetic variations in a wide variety of plant species.In this study,we created a million-scale EMS population(MEP)that started with the Chinese wheat cultivars‘Luyan 128’,‘Jimai 38’,‘Jimai 44’,and‘Shannong 30’.In the M1 generation,the MEP had numerous phenotypical variations,such as>3,000 chlorophyll-deficient mutants,2,519 compact spikes,and 1,692 male sterile spikes.There were also rare mutations,including 30 independent tillers each with double heads.Some M1 variations of chlorophyll-deficiency and compact spikes were inheritable,appearing in the M2 or M3 generations.To advance the entire MEP to higher generations,we adopted a single-seed descendent(SSD)approach.All other seed composites of M2 were used to screen other agronomically important traits,such as the tolerance to herbicide quizalofop-P-methyl.The MEP is available for collaborative projects,and provides a valuable toolbox for wheat genetics and breeding for sustainable agriculture.展开更多
A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary...A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary mechanistic studies indicated that the reaction probably underwent a Cu-catalyzed formal C–H insertion to produce an allene intermediate, which was then trapped by a sulfonyl anion to give the corresponding product.展开更多
An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reacti...An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.展开更多
Herein,we report a novel heterogeneous photocatalyst for radical-mediated oxidative oxysulfonylation of alkynes toβ-keto sulfones under environmentally benign conditions.The oxygen vacancy-rich semiconductor Nb2O5(la...Herein,we report a novel heterogeneous photocatalyst for radical-mediated oxidative oxysulfonylation of alkynes toβ-keto sulfones under environmentally benign conditions.The oxygen vacancy-rich semiconductor Nb2O5(labeled as OVs-N-Nb_(2)O_(5))could efficiently catalyze a wide range of alkynes,especially for those bearing electron-deficient substituents or internal alkynes,to their correspondingβ-keto sulfones in good to high yields with good tolerance of diverse functional groups under visible-light illumination.The late-stage modification of steroidal compounds and synthesis of bioactive molecules were also achieved via this procedure,highlighting its potential for practical applications.Meanwhile,the photocatalyst OVs-N-Nb_(2)O_(5) showed outstanding catalytic stability for successive recycles without appreciable loss in activity and selectivity.The critical role of oxygen vacancies on improving reaction activity and selectivity was clearly disclosed via control experiments and theoretical calculation.展开更多
A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted ...A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted under catalyst-and additive-free conditions,in which C-S and C-C bonds were selectively constructed in one-pot procedure.展开更多
In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides an...In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides and allyl alcohol under aqueous conditions to afford selenocarbamates and allyl sulfone compounds is reported.The sulfinic acid as the first-step side product is converted to the allyl sulfone compound by water promoted reaction with allyl alcohol.Water acts as both an oxygen source of selenocarbamates and as a promoter to drive the second step reactio n.The reactions have the advantages of mild conditions,green,environment-friendly,and high atomic economy.展开更多
文摘Abstract: We described the synthesis of two 5-substituted γ-lactams Ⅰand Ⅱ by sulfone-baaed α-amidoalkylation method. This constitiutes the formal synthesis of ant venom alkaloids 2 and 3 in racemic form. The key intermediate 18 for the chiral synthesis of 2 and 3 was prepared from new chiral sulfone 7 by the same method.
基金We are grateful to the National Natural Science Foundation of China (Nos. 20332060 and 2472072)
文摘One novel carbon-carbon bond insertion reaction of arynes has been developed. By this reaction β-keto sulfones can insert the triple bond of arynes to prepare polysubstituted ortho-keto benzyl sulfones.
文摘Arenesulfonyl chloride undergoes a facile one-pot coupling reaction with active halides assisted by zinc to give the corresponding sulfones in acceptable yields.
基金the Municipal Government of Shanghai(No.03DZ19209)Shanghai Hua-Yi Group for financial support.
文摘The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfinic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.
基金the National Natural Science Foundation of China(No.20462002)Natural Science Foundation of Jiangxi Province(No.0420015)for financial support.
文摘(E)-α-Iodovinyl sulfones 1 underwent the Sonogashira coupling reactions with terminal alkynes 2 in piperidine at room temperature in the presence of 5 mol% of Pd(PPh3)4 and 10 mol% of CuI to stereospecifically afford the corresponding (Z)-2-sulfonyl-substituted 1,3-enynes 3 in high yields.
基金supported by the Science and Technology Project of Zhejiang Province(2016C33039)the Public Technology Research Project(Analysis and Measurement)of Zhejiang Province(LGC19B070004)+1 种基金State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences(KF2018-15)Natural Science Foundation of Zhejiang Province(LY18C030003)
文摘Polychlorinated dibenzothiophenes(PCDTs)and their corresponding sulfone(PCDTO2)compounds are a group of important persistent organic pollutants.In the present study,geometrical optimization and subsequent calculations of electrostatic potentials(ESPs)on molecular surface have been performed for all 135 PCDTs and 135 PCDTO2 congeners at the HF/6-31G*level of theory.A number of statistically-based parameters have been extracted.Linear relationship between gas-chromatographic retention index(RI)and the structural descriptors have been established by multiple linear regression.The result shows that two descriptors derived from positive electrostatic potential on molecular surface,σ+^2 andπ,together with the molecular volume(Vmc)and the energy of the lowest unoccupied molecular orbital(ELUMO)can be well used to express the quantitative structure-retention relationship(QSRR)of PCDTs and PCDTO2.Predictive capability of the two models has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient(RCV)of 0.996 and 0.997,respectively.Furthermore,the predictive power of the models is further examined for the external test set.Correlation coefficients(R)between the observed and predicted RI values for the external test set are 0.997 and0.998,respectively,validating the robustness and good prediction of our model.The QSRR model established may provide again a powerful method for predicting chromatographic properties of aromatic organosulfur compounds.
基金supported by the National Natural Science Foundation of China(22171206)the Natural Science Foundation of Zhejiang Province(Z23B020002,LY22B020003,)+1 种基金the Open Foundation of Hunan Provincial Key Laboratory of Controllable Preparation and Functional Application of Fine Polymers(E22307)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2020ZD04)。
文摘β-Chiral sulfones are structural motifs widely found in natural products and bioactive molecules, while also serving as important intermediates for the synthesis of valuable chiral scaffolds. In contrast to the rapid growth of sulfur dioxide insertion chemistry over the last decade, enantioselective catalytic variants for accessing β-chiral sulfones, especially those bearing a quaternary carbon stereocenter, remain rare. Herein, we report an enantioselective copper/bisoxazoline catalyzed oxysulfonylation of alkenes to yield isoxazolinyl-containing β-chiral sulfones bearing quaternary carbon stereocenters with moderate to excellent yields and up to 96:4 er. The advantage and irreplaceability of this sulfur dioxide insertion catalytic system have been demonstrated by achieving transformations clearly unavailable with the previously reported sulfonyl chloride system. Additionally,the recoverability of the new-developed bisoxazoline ligand L9 and its reusability without any erosion of the catalytic activity and enantioselectivity further demonstrate the usefulness of the protocol.
基金financial support from the Natural Science Foundation of China and Shandong Province(Nos.21971149,92156007,ZR2019ZD45,ZR2020KB005)the Fundamental Research Funds of Shandong University。
文摘A new,four component copper(Ⅰ)-catalyzed interrupted click/radical relay cascade has been developed.This unprecedented interrupted click reaction provides a rapid modular synthesis of triazole sulfones,important privileged heterocyclic pharmacophores which cannot be accessed by a traditional click reaction.Radical interception of cuprate-triazole,the key reaction intermediate formed in situ,is an important feature of this process.
基金Financial support from the National Natural Science Foundation of China(No.21901041)the Fuzhou University(No.0041/511095)。
文摘As an attractive C1 synthon,carbon dioxide(CO_(2))has been extensively used in organic synthesis to produce carboxylic acids.In this research,stereoselective electrochemical carboxylation ofα,β-unsaturated sulfones has been developed under transition-metal-free conditions.All the cinnamic acids and the derivatives are obtained selectively in the E-configuration.Besides,arylpropiolates also can be produced from alkynyl sulfones.
文摘The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.
基金financially supported by National Natural Science Foundation of China(No.82204604,22304055)Youth Talent Program of Hebei Provincial Education Department(No.BJ2018020)+1 种基金Natural Science Foundation of Hebei Province(No.E2020209151,E2022209158,H2022209012)Science and Technology Project of Hebei Education Department(No.JZX2024026)。
文摘Aqueous zinc ion batteries(AZIBs)are one of the promising energy storage devices.However,uncontrolled dendrite and side reactions have seriously hindered its further application.In this study,the metal-organic framework(MOF)functionalized glass fiber separator(GF-PFC-31)was used to regulate interfacial behavior of zinc metal anode,enabling the development of high-performance AZIBs.In PFC-31,there areπ-πinteractions between two adjacent benzene rings with a spacing of 3.199 A.This spacing can block the passage of[Zn(H_(2)O)_6]^(2+)(8.6 A in diameter)through the GF-PFC-31 separator to a certain extent,which promotes the deposition process of Zn ions.In addition,the sulfonic acid group(-S03H)contained in GF-PFC-31 can form a hydrogen bonding network with H_(2)O,which can provide a desolvation effect and reduce the side reaction.Consequently,GF-PFC-31 separator achieves uniform deposition of Zn ions.The Zn‖GF-PFC-31‖Zn symmetric cell exhibits stable cycle life(3000 h at 1.2 mA cm^(-2),2000 h at 0.3 mA cm^(-2),and 2000 h at 5.0 mA cm^(-2)),and Zn‖GF-PFC-31‖MnO_(2) full cell with GF-PFC-31 separator can cycle for 1000 cycles at 1.2 A g^(-1)with capacity retention rate of 82.5%.This work provides a promising method to achieve high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(51978133,52100026,U20A20322,52170151,51978132)the Fundamental Research Funds for the Central Universities of China(2412021QD022)+1 种基金the Key Research and Development Project of Hainan Province(ZDYF2022SHFZ298)the Industrialization Cultivation Project of Jilin Provincial Department of Education(JJKH20221174CY)。
文摘The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.
基金This work was supported by the National Key Research and Development Program of China(2022YFF1002300)the Quancheng‘5150’Talent Program,China(07962021047)the Agriculture Applied Technology Initiative of Jinan Government,China(CX202113).
文摘Wheat germplasm is a fundamental resource for basic research,applied studies,and wheat breeding,which can be enriched normally by several paths,such as collecting natural lines,accumulating breeding lines,and introducing mutagenesis materials.Ethyl methane sulfonate(EMS)is an alkylating agent that can effectively introduce genetic variations in a wide variety of plant species.In this study,we created a million-scale EMS population(MEP)that started with the Chinese wheat cultivars‘Luyan 128’,‘Jimai 38’,‘Jimai 44’,and‘Shannong 30’.In the M1 generation,the MEP had numerous phenotypical variations,such as>3,000 chlorophyll-deficient mutants,2,519 compact spikes,and 1,692 male sterile spikes.There were also rare mutations,including 30 independent tillers each with double heads.Some M1 variations of chlorophyll-deficiency and compact spikes were inheritable,appearing in the M2 or M3 generations.To advance the entire MEP to higher generations,we adopted a single-seed descendent(SSD)approach.All other seed composites of M2 were used to screen other agronomically important traits,such as the tolerance to herbicide quizalofop-P-methyl.The MEP is available for collaborative projects,and provides a valuable toolbox for wheat genetics and breeding for sustainable agriculture.
基金supported by the National Natural Science Foundation of China(21432009,21672200,21472177,21772185,21801233)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)
文摘A copper-catalyzed 1,1-difunctionalization of terminal alkynes was achieved via a three-component reaction, providing a variety of vinyl sulfones with good yields and excellent chemo-and stereoselectivity. Preliminary mechanistic studies indicated that the reaction probably underwent a Cu-catalyzed formal C–H insertion to produce an allene intermediate, which was then trapped by a sulfonyl anion to give the corresponding product.
基金Financial support was provided by Hong Kong RGC (No. 16302318)Shenzhen Science and Technology Innovation Committee (No. JCYJ20170818113708560)HKUST (No. IEG17SC03)
文摘An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.
基金supportof the National Natural Science Foundation of China(Nos.22002178,22078350)the Natural Science Foundation of Shandong Province(ZR2020KB016)+1 种基金Shandong Energy Institute Fund(Grant No.SEll202138)Y.Y.alsothanks the Royal Society(UK)fora Newton Advanced Fellowship(NAF/R2/180695).
文摘Herein,we report a novel heterogeneous photocatalyst for radical-mediated oxidative oxysulfonylation of alkynes toβ-keto sulfones under environmentally benign conditions.The oxygen vacancy-rich semiconductor Nb2O5(labeled as OVs-N-Nb_(2)O_(5))could efficiently catalyze a wide range of alkynes,especially for those bearing electron-deficient substituents or internal alkynes,to their correspondingβ-keto sulfones in good to high yields with good tolerance of diverse functional groups under visible-light illumination.The late-stage modification of steroidal compounds and synthesis of bioactive molecules were also achieved via this procedure,highlighting its potential for practical applications.Meanwhile,the photocatalyst OVs-N-Nb_(2)O_(5) showed outstanding catalytic stability for successive recycles without appreciable loss in activity and selectivity.The critical role of oxygen vacancies on improving reaction activity and selectivity was clearly disclosed via control experiments and theoretical calculation.
基金supported by the International Cooperation Project of Qinghai Province(No.2018-HZ-806)the Youth Innovation and Technology Project of Higher School in Shandong Province(No.2019KJC021)+3 种基金the Natural Science Foundation of Shandong Province(No.ZR2018MB009)the Qinghai Key Laboratory of Tibetan Medicine Research(No.2017ZJ-Y11)CAS“Light of West China”Program 2018Entrepreneurship Training Program for College Students(No.201910049)。
文摘A convenient and regioselective sulfonylation/cyclization of 1,6-enynes with arylazo sulfones has been developed to access a series of sulfonylated γ-butyrolactams.The present reaction could be efficiently conducted under catalyst-and additive-free conditions,in which C-S and C-C bonds were selectively constructed in one-pot procedure.
基金the National Natural Science Foundation of China (Nos.21971174,21772137,21672157)the Ph.D.Programs Foundation of PAPD+2 种基金the Project of Scientific and Technologic Infrastructure of Suzhou (No.SZS201708)the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (No. 16KJA150002)Soochow University,and State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials for financial support。
文摘In many reactions involving selenosulfonate or thiosulfonate,the sutfone group often leaves in form of benzenesutfinic acid or sodium benzenesulfinate.A one-pot two-step reaction of selenosulfonate with isocyanides and allyl alcohol under aqueous conditions to afford selenocarbamates and allyl sulfone compounds is reported.The sulfinic acid as the first-step side product is converted to the allyl sulfone compound by water promoted reaction with allyl alcohol.Water acts as both an oxygen source of selenocarbamates and as a promoter to drive the second step reactio n.The reactions have the advantages of mild conditions,green,environment-friendly,and high atomic economy.