Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions....Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.展开更多
Facile synthetic routes for the preparation of some new 4-amino-3,5-dinitropyridine derivatives have been revealed. Nitration of 2-chloropyridin-4-amine （1） as a starting material, in an unexpected one-step reaction...Facile synthetic routes for the preparation of some new 4-amino-3,5-dinitropyridine derivatives have been revealed. Nitration of 2-chloropyridin-4-amine （1） as a starting material, in an unexpected one-step reaction, to give dinitrated derivatives, followed by nucleophilic substitution reactions with sodium azide, potassium fluoride, ammonia, methylamine, and 4-nitroimidazol, respectively, gave substituted 4-amino-3,5-dinitropyridine derivatives. Meanwhile, its azide derivative underwent a ring closure conversion into 7-amino-6-nitro-[1,2,5]oxadiazolo[3,4-b]- pyridine-1-oxide. It is of significance that all of the nucleophilic substitution reactions were carried out under mild conditions.展开更多
The catalytic activity ofβ-cyclodextrin immobilized on Dowex resin as an efficient solid-liquid phase transfer catalyst was developed for the synthesis of alkyl thiocyanates and phenacyl derivatives in water. The nuc...The catalytic activity ofβ-cyclodextrin immobilized on Dowex resin as an efficient solid-liquid phase transfer catalyst was developed for the synthesis of alkyl thiocyanates and phenacyl derivatives in water. The nucleophilic substitution reactions were performed under mild reaction condition and gave the products in excellent yields. Fur thermore, the catalyst could be recycled by facile separation without any loss of activity.展开更多
We analysed the photooxidation reaction in the electro-(1O2) and nucleophilic (O2•−) reaction of 2-pyridone azo derivatives. First, we calculated the energy (enthalpies) of tautomers formation, which is a measure of d...We analysed the photooxidation reaction in the electro-(1O2) and nucleophilic (O2•−) reaction of 2-pyridone azo derivatives. First, we calculated the energy (enthalpies) of tautomers formation, which is a measure of durability and the probability of their formation. We performed the light fastness calculations of the monoazopyridone dyes. Using the semi-empirical methods of quantum chemistry AM1 and PM3, the reactivity indicators of superdelocalisability (SrE(N)) and the electron density distribution in ground state on the highest occupied HOMO orbital and the lowest unoccupied excited state LUMO in 2-pyridone phenylazo derivatives were calculated. Superdelocalisability coefficients enable the stability to oxidising agents of various chemical molecules depending on the tautomeric forms in which they may occur. The results of the electron density calculations at the HOMO and LUMO boundary orbitals allow to determine the tendency to electrophilic attack with singlet oxygen 1O2 or nucleophilic attack of the superoxide anion O2•−on a specific atom in the molecule. The structure of the dyes was optimised with MM+, MD and AM1 or PM3 until a constant energy value was achieved with a convergence criterion of 0.01 kcal/mol.展开更多
Treatment of osmapentalyne [Os { ≡C-C（COOMe）=CH-C =CH-C（PPh3） =CH-}Cl（PPh3）2]＋ BF4-with arylamines in the presence of Cs2CO3 produced osmium-bridged polycyclic aromatic complexes.In this reaction,metal carbyne...Treatment of osmapentalyne [Os { ≡C-C（COOMe）=CH-C =CH-C（PPh3） =CH-}Cl（PPh3）2]＋ BF4-with arylamines in the presence of Cs2CO3 produced osmium-bridged polycyclic aromatic complexes.In this reaction,metal carbyne of osmapentalyne was first attacked by nucleophiles,followed by a C-H oxidative addition.The UV-Vis spectra of these osmium-bridged polycyclic aromatic complexes were measured.The result shows that these osmium-bridged polycyclic aromatic complexes have broad absorption in the UV-Vis region up to 650 nm.展开更多
Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high se...Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high sensitivity and selectively and invasive on-time imaging.However,the similar structures and reactivity of these biothiols present great challenges for selective detection.This review focused on the the "aromatic nucleophilic substitution-rearrangement(SNAr-rearrangement) mechanism",which provided a powerful tool to design fluorescent probes for the discrimination between biothiols.We classify the fluorescent probes according to types of fluorophores,such as difluoroboron dipyrromethene(BODIPY),nitrobenzoxadiazole(NBD),cyanine,pyronin,naphthalimide,coumarin,and so on.We hope this review will inspire exploration of new fluorescent probes for biothiols and other relevant analytes.展开更多
Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem as...Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.展开更多
Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an o...Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an osmapentalyne with benzyl carbanions,was developed.The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond,followed by C—H activation to form the five-membered osmacyclopentadiene ring.Most of the reactions were carried out at room temperature,the substituents on the aromatic rings of benzyl carbanions are diverse,and the resulting products contain an Os—H bond,representing a novel type of 10C-carbolong complexes.This work provides a new convenient route to construct metallacyclopentadienes,which is expected to further promote the development of such a type of substances.展开更多
MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still chal...MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still challenges in modifying the surface functional groups of MXene to further improve the electrochemical performance and increase the structure variety for MXene-based sulfur host.Herein,we report an efficient and flexible nucleophilic substitution(S_(N))strategy to modify the Ti_(3)C_(2)T_(x) surface terminations and purposefully designed Magnolol-modified Ti_(3)C_(2)T_(x)(M-Ti_(3)C_(2)T_(x))as powerful cathode host materials.Benefiting from more C-Ti-O bonds forming and diallyl groups terminations reducing after the dehalogenation and nucleophilic addition reactions,the given M-Ti_(3)C_(2)T_(x) electrode could effectively suppress the lithium polysulfides shuttling via chemisorption and C—S covalent bond formation.Besides,the Magnolol-modified Ti_(3)C_(2)T_(x) significantly accelerates polysulfide redox reaction and reduces the activation energy of Li_(2) S decomposition.As a result,the as-prepared M-Ti_(3)C_(2)T_(x) electrode displays an excellent rate capability and a high reversible capacity of 7.68 mAh cm^(-2)even under 7.2 mg cm^(-2)S-loaded with a low decay rate of 0.07%(from 2 nd cycle).This flexible surface-modified strategy for MXene terminations is expected to be extended to other diverse MXene applications.展开更多
Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful s...Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.展开更多
Atroposelective construction of axially chiral alkene-heteroaryl scaffolds is highly desired but challenging.In this work,we established an atroposelective construction of axially chiral alkene-indole scaffolds via th...Atroposelective construction of axially chiral alkene-heteroaryl scaffolds is highly desired but challenging.In this work,we established an atroposelective construction of axially chiral alkene-indole scaffolds via the strategy of catalytic enantioselective addition reaction of 3-alkynyl-2-indolylmethanols with bulky nucleophiles.展开更多
As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation sid...As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.展开更多
In this letter,a mild and efficient procedure for synthesis of phenacyl derivatives under homogenous catalysis in the presence of tetrabutylammonium bromide in aqueous media is described.The nucleophilic substitution ...In this letter,a mild and efficient procedure for synthesis of phenacyl derivatives under homogenous catalysis in the presence of tetrabutylammonium bromide in aqueous media is described.The nucleophilic substitution reactions were performed under ecofriendly conditions and gave the corresponding products in high yields and short reaction times.展开更多
The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of ar...The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.展开更多
Under neat conditions,an efficient method for synthesis of imidoesters has been developed using cyanatobenzenes and dicarbonyl compounds.Nucleophilic addition spontaneously occurred between the two kinds of materials ...Under neat conditions,an efficient method for synthesis of imidoesters has been developed using cyanatobenzenes and dicarbonyl compounds.Nucleophilic addition spontaneously occurred between the two kinds of materials at room temperature with yields of up to 90%.A mechanism directed towards to the imidoester formation has been proposed.展开更多
Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4...Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4-trisubstituted cyclobutanones from readily available dichlorocyclobutanones.The substitution reaction proceeds smoothly via oxyallyl cation intermediates under mild basic conditions.Further transformation to the synthesis of 1,2,3,4-tetrasubstituted cyclobutanes was also explored.展开更多
An efficient method for the synthesis of α-phenylcinnamates via silver catalyzed C—C bond activation reaction of cyclopropenone and alcohol was developed.This protocol features a simple reaction system,specific regi...An efficient method for the synthesis of α-phenylcinnamates via silver catalyzed C—C bond activation reaction of cyclopropenone and alcohol was developed.This protocol features a simple reaction system,specific regioselectivity,good functional group compatibility and good yields.It is of great significance for the later modification of natural products.展开更多
Electrochemical water splitting plays a crucial role in storing sustainable energy into H2 as an ideal fuel,in which the anodic oxygen evolution reaction(OER)is the bottleneck.Currently,Fe-doped NiOOH(Ni_(1−x)Fe_(x)OO...Electrochemical water splitting plays a crucial role in storing sustainable energy into H2 as an ideal fuel,in which the anodic oxygen evolution reaction(OER)is the bottleneck.Currently,Fe-doped NiOOH(Ni_(1−x)Fe_(x)OOH)is a promising OER catalyst under alkaline conditions.However,the specific active sites responsible for their good performances remain debatable.Here,we identify a nickel-oxygen radical(Ni–O·)and an iron-oxo(Fe=O)group as two essential states for adsorbed oxygen.Meanwhile,both thermochemical O–O coupling and electrochemical OER elementary steps are considered on the Ni_(1−x)Fe_(x)OOH catalysts.Sophisticated mechanistic studies with a combined density functional theory simulation and experimental analysis unravel that both the Ni and Fe centers can act as the active sites for the defective Ni_(1−x)Fe_(x)OOH to catalyze OER,depending on the nature of the defect.The presence of Fe can benefit the stabilization of the defective surface and influence the electronic property of the nearby Ni site.This work not only identifies the intrinsic active sites of Ni_(1−x)Fe_(x)OOH,but also illustrates the essential roles of defects in catalysis,which sheds light on the design of more efficient OER catalysts in the future.展开更多
文摘Cross-linked poly（diallyldimethylammonium chloride） and its derivative copolymers were synthesized and used as phase transfer catalyst in the nucleophilic substitution reaction especially halogen exchange reactions.In addition,the effect of hydrophilic-hydrophobic character of the polymers in the nucleophilic reactions was investigated.
文摘Facile synthetic routes for the preparation of some new 4-amino-3,5-dinitropyridine derivatives have been revealed. Nitration of 2-chloropyridin-4-amine （1） as a starting material, in an unexpected one-step reaction, to give dinitrated derivatives, followed by nucleophilic substitution reactions with sodium azide, potassium fluoride, ammonia, methylamine, and 4-nitroimidazol, respectively, gave substituted 4-amino-3,5-dinitropyridine derivatives. Meanwhile, its azide derivative underwent a ring closure conversion into 7-amino-6-nitro-[1,2,5]oxadiazolo[3,4-b]- pyridine-1-oxide. It is of significance that all of the nucleophilic substitution reactions were carried out under mild conditions.
文摘The catalytic activity ofβ-cyclodextrin immobilized on Dowex resin as an efficient solid-liquid phase transfer catalyst was developed for the synthesis of alkyl thiocyanates and phenacyl derivatives in water. The nucleophilic substitution reactions were performed under mild reaction condition and gave the products in excellent yields. Fur thermore, the catalyst could be recycled by facile separation without any loss of activity.
文摘We analysed the photooxidation reaction in the electro-(1O2) and nucleophilic (O2•−) reaction of 2-pyridone azo derivatives. First, we calculated the energy (enthalpies) of tautomers formation, which is a measure of durability and the probability of their formation. We performed the light fastness calculations of the monoazopyridone dyes. Using the semi-empirical methods of quantum chemistry AM1 and PM3, the reactivity indicators of superdelocalisability (SrE(N)) and the electron density distribution in ground state on the highest occupied HOMO orbital and the lowest unoccupied excited state LUMO in 2-pyridone phenylazo derivatives were calculated. Superdelocalisability coefficients enable the stability to oxidising agents of various chemical molecules depending on the tautomeric forms in which they may occur. The results of the electron density calculations at the HOMO and LUMO boundary orbitals allow to determine the tendency to electrophilic attack with singlet oxygen 1O2 or nucleophilic attack of the superoxide anion O2•−on a specific atom in the molecule. The structure of the dyes was optimised with MM+, MD and AM1 or PM3 until a constant energy value was achieved with a convergence criterion of 0.01 kcal/mol.
文摘Treatment of osmapentalyne [Os { ≡C-C（COOMe）=CH-C =CH-C（PPh3） =CH-}Cl（PPh3）2]＋ BF4-with arylamines in the presence of Cs2CO3 produced osmium-bridged polycyclic aromatic complexes.In this reaction,metal carbyne of osmapentalyne was first attacked by nucleophiles,followed by a C-H oxidative addition.The UV-Vis spectra of these osmium-bridged polycyclic aromatic complexes were measured.The result shows that these osmium-bridged polycyclic aromatic complexes have broad absorption in the UV-Vis region up to 650 nm.
基金financially supported by the National Natural Science Foundation of China (No. 21525206)
文摘Biothiols,including cysteine(Cys),homocysteine(Hey),and glutathione(GSH) play important roles in physiological processes,and the detection of thiol using fluorescent probes has attracted attention due to their high sensitivity and selectively and invasive on-time imaging.However,the similar structures and reactivity of these biothiols present great challenges for selective detection.This review focused on the the "aromatic nucleophilic substitution-rearrangement(SNAr-rearrangement) mechanism",which provided a powerful tool to design fluorescent probes for the discrimination between biothiols.We classify the fluorescent probes according to types of fluorophores,such as difluoroboron dipyrromethene(BODIPY),nitrobenzoxadiazole(NBD),cyanine,pyronin,naphthalimide,coumarin,and so on.We hope this review will inspire exploration of new fluorescent probes for biothiols and other relevant analytes.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29672004)
文摘Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]^(20),IR,~1H NMR,^(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.
基金the NSFC(Nos.22071098,21931002 and 22101123)the Guangdong Provincial Key Laboratory of Catalysis(No.2020B121201002)+2 种基金the Shenzhen Science and Technology Innovation Committee(No.JCYJ20200109140812302)Introduction of Major Talent Projects in Guangdong Province(No.2019CX01C079)Outstanding Talents Training Fund in Shenzhen,for their financial support.
文摘Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions,therefore,new methods to achieve them are anticipated.In this study,a formal[3+2]method,through the reactions of an osmapentalyne with benzyl carbanions,was developed.The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond,followed by C—H activation to form the five-membered osmacyclopentadiene ring.Most of the reactions were carried out at room temperature,the substituents on the aromatic rings of benzyl carbanions are diverse,and the resulting products contain an Os—H bond,representing a novel type of 10C-carbolong complexes.This work provides a new convenient route to construct metallacyclopentadienes,which is expected to further promote the development of such a type of substances.
基金the support from CNPC Innovation Found(2021DQ02-1001)Liao Ning Revitalization Talents Program(XLYC1907144)Xinghai Talent Cultivation Plan(X20200303)。
文摘MXene-based materials have gained considerable attention for lithium-sulfur(Li-S)batteries cathode materials due to their superior electric conductivity and high affinitive to polysulfides.However,there are still challenges in modifying the surface functional groups of MXene to further improve the electrochemical performance and increase the structure variety for MXene-based sulfur host.Herein,we report an efficient and flexible nucleophilic substitution(S_(N))strategy to modify the Ti_(3)C_(2)T_(x) surface terminations and purposefully designed Magnolol-modified Ti_(3)C_(2)T_(x)(M-Ti_(3)C_(2)T_(x))as powerful cathode host materials.Benefiting from more C-Ti-O bonds forming and diallyl groups terminations reducing after the dehalogenation and nucleophilic addition reactions,the given M-Ti_(3)C_(2)T_(x) electrode could effectively suppress the lithium polysulfides shuttling via chemisorption and C—S covalent bond formation.Besides,the Magnolol-modified Ti_(3)C_(2)T_(x) significantly accelerates polysulfide redox reaction and reduces the activation energy of Li_(2) S decomposition.As a result,the as-prepared M-Ti_(3)C_(2)T_(x) electrode displays an excellent rate capability and a high reversible capacity of 7.68 mAh cm^(-2)even under 7.2 mg cm^(-2)S-loaded with a low decay rate of 0.07%(from 2 nd cycle).This flexible surface-modified strategy for MXene terminations is expected to be extended to other diverse MXene applications.
基金support from the National Key R&D Program of China (2022YFA1503703,2021YFF0701604)the National Natural Science Foundation of China (21825105,22231004,22271135)+1 种基金Guangdong Innovative Program (2019BT02Y335)Shenzhen Science and Technology Program (KQTD20210811090112004,JCYJ20210324120205016,JCYJ20210324105005015).
文摘Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21772069 and 21831007)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX20_2235)the Natural Science Foundation of JSNU(No.19XSRX013)。
文摘Atroposelective construction of axially chiral alkene-heteroaryl scaffolds is highly desired but challenging.In this work,we established an atroposelective construction of axially chiral alkene-indole scaffolds via the strategy of catalytic enantioselective addition reaction of 3-alkynyl-2-indolylmethanols with bulky nucleophiles.
基金supported by the National Natural Science Foundation of China (21720102003, 91534203 and 21522607)the Fundamental Research Funds for the Central Universities (WK2060190072 and WK2340000066)
文摘As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.
基金Partial support for this work by Islamic Azad University,Mahshahr branch research council
文摘In this letter,a mild and efficient procedure for synthesis of phenacyl derivatives under homogenous catalysis in the presence of tetrabutylammonium bromide in aqueous media is described.The nucleophilic substitution reactions were performed under ecofriendly conditions and gave the corresponding products in high yields and short reaction times.
文摘The (Et_4N)_2[Fe_4(SPh)_10] stimulated reaction of α-bromonaphthalene with pinacolone carbanion in DMSO leads to the formation of 1-(α-naphthyl)pinacolone. The reaction is suggested in terms of SRN1 mechanism of aromatic nucleophillic substitution and has potential value in synthesis to obtain (-substituted naphthalene derivaties.
基金the National Natural Science Foundation of China (Nos.21372265 and 61271059)the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry,the Natural Science Foundation Project of CQ CSTC (Nos.CSTC2013jcyjA0217 and CSTC2010BB4086)the Fundamental Research Funds for the Central Universities(Nos.CQDXWL2013-Z012 and CDJZR-14225502)
文摘Under neat conditions,an efficient method for synthesis of imidoesters has been developed using cyanatobenzenes and dicarbonyl compounds.Nucleophilic addition spontaneously occurred between the two kinds of materials at room temperature with yields of up to 90%.A mechanism directed towards to the imidoester formation has been proposed.
基金supported by the National Natural Science Foundation of China(22071028,21921003).
文摘Stereoselective synthesis of multi-substituted cyclobutanes with different substituents is still a daunting challenge in organic synthesis.We report here a practical and facile approach to synthesizing all-trans 2,3,4-trisubstituted cyclobutanones from readily available dichlorocyclobutanones.The substitution reaction proceeds smoothly via oxyallyl cation intermediates under mild basic conditions.Further transformation to the synthesis of 1,2,3,4-tetrasubstituted cyclobutanes was also explored.
基金Project supported by the National Natural Science Foundation of China(No.21702160)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(No.KF2311)。
文摘An efficient method for the synthesis of α-phenylcinnamates via silver catalyzed C—C bond activation reaction of cyclopropenone and alcohol was developed.This protocol features a simple reaction system,specific regioselectivity,good functional group compatibility and good yields.It is of great significance for the later modification of natural products.
文摘Electrochemical water splitting plays a crucial role in storing sustainable energy into H2 as an ideal fuel,in which the anodic oxygen evolution reaction(OER)is the bottleneck.Currently,Fe-doped NiOOH(Ni_(1−x)Fe_(x)OOH)is a promising OER catalyst under alkaline conditions.However,the specific active sites responsible for their good performances remain debatable.Here,we identify a nickel-oxygen radical(Ni–O·)and an iron-oxo(Fe=O)group as two essential states for adsorbed oxygen.Meanwhile,both thermochemical O–O coupling and electrochemical OER elementary steps are considered on the Ni_(1−x)Fe_(x)OOH catalysts.Sophisticated mechanistic studies with a combined density functional theory simulation and experimental analysis unravel that both the Ni and Fe centers can act as the active sites for the defective Ni_(1−x)Fe_(x)OOH to catalyze OER,depending on the nature of the defect.The presence of Fe can benefit the stabilization of the defective surface and influence the electronic property of the nearby Ni site.This work not only identifies the intrinsic active sites of Ni_(1−x)Fe_(x)OOH,but also illustrates the essential roles of defects in catalysis,which sheds light on the design of more efficient OER catalysts in the future.
