Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP)...Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP),and hybrid polymerization(HP)has been a charming research direction.Herein,we synthesized a novel cationic macro-PI(P-CSS)by copolymerizing polymerizable coumarin sulfonium salt(CSS)and methyl methacrylate(MMA).Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain.Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365,405 nm and under Laser@980 nm(with upconversion particles,UCPs).The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate(TMTPA)polymer is 1.25%of CSS,and in 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate(EPOX)polymer is 1.96%.These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.展开更多
Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, d...Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.展开更多
A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described.And a broad range of difluoromthyl enol ethers...A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described.And a broad range of difluoromthyl enol ethers were readily accessed in good to excellent yields under mild reaction conditions.Mechanistic studies revealed that the O-difluoromethylation reaction proceeds mainly via a difluorocarbene pathway.展开更多
Two electrophilic pentafluoroethylating reagents of pentafluoroethyl(p-methylphenyl)sulfonium bis(carbometh-oxy)methylide(4a)and pentafluoroethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide(4b),and their reacti...Two electrophilic pentafluoroethylating reagents of pentafluoroethyl(p-methylphenyl)sulfonium bis(carbometh-oxy)methylide(4a)and pentafluoroethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide(4b),and their reactions under mild conditions withβ-ketoesters,aryl iodides and heteroaromatics are described.展开更多
A series of D-π-A type sulfonium salt photoacid generators with different π-conjugated structures, such as triphenyl, phenylstilbene, styryl-biphenyl, and stilbene, were designed to determine the effect of molecular...A series of D-π-A type sulfonium salt photoacid generators with different π-conjugated structures, such as triphenyl, phenylstilbene, styryl-biphenyl, and stilbene, were designed to determine the effect of molecular structures on the photochemical and photophysical properties. The mechanisms of photochemical generation of H＋ were studied by UV-Vis spectroscopy, theoretical calculations, and fluorescence spectroscopy. It is found that the frontier orbits determine the absorption, the molar extinction coefficients, and the quantum yields of photoacid generation. Triphenyl systems connected with sulfonium are beneficial to increase the quantum yields of acid generation. The photoreactivity of four sulfonium salts was further evaluated through the polymerizations of various epoxide monomers at different irradiation wavelengths （365- 425 nm） by using the real-time infrared spectroscopy with light-emitting diodes. The high quantum yields for acid generation （ФH＋ = -0.32 to 0.58） and the high molar extinction coefficients （ε = -23500 L.mol-1.cm-1 to 31000 L.mol-1.cm-1） of the sulfonium salts lead to high conversion rates （over 50%-80%）. Hence, these photoinitiators exhibit potential for the photocuring applications.展开更多
To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chit...To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chitosan(MCMCS),Ethyl sulfi de carboxymethyl chitosan(ECMCS),Propyl sulfi de carboxymethyl chitosan(PCMCS),and Butyl sulfi de carboxymethyl chitosan(BCMCS).To determine the structure of the new class of the derivatives,methods of the Fourier transform infrared spectroscopy(FT-IR),^(1)H nuclear magnetic resonance spectrometer(^(1)H NMR),and^(13)C nuclear magnetic resonance spectrometer(^(13)C NMR)were used.Moreover,the antioxidant activity of the derivatives for three types of free radicals,i.e.,hydroxyl radical,superoxide radical,and 1,1-diphenyl-2-picrylhydrazyl(DPPH)radical was evaluated in vitro.In addition,the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay.The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL,with scavenging rate of over 70%and some up to 100%.At this high rate,the overall cell viability in the toxicity test reached more than 80%,indicating that the synthetic derivative had a little cytotoxicity.The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan,and the combination of sulfonate ions with diff erent chain lengths further enhanced the antioxidant activity of chitosan.Therefore,the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food,biomedicine,and medical fi elds.展开更多
The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in ...The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in an acidic solution under atmosphericconditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acety-lacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen ox-idative polymerization. The polymerization mechanism involves multielectron oxidation ofthe sulfides followed by successive electrophilic substitution. The resulting polyarylenesul-fonium cations are useful as a soluble precursor for the synthesis of high molecular weight(M_w>10~5) poly(thio arylne)s.展开更多
Sulfonium salts and sulfur ylides are important S(Ⅳ) motifs,and have displayed many unique reactivities to provide simple,effective,and often stereoselective synthesis toward sulfur containing compounds.Impressive de...Sulfonium salts and sulfur ylides are important S(Ⅳ) motifs,and have displayed many unique reactivities to provide simple,effective,and often stereoselective synthesis toward sulfur containing compounds.Impressive developments have been witnessed within this field during the past several years.In light of the increasing demand of organosulfur compounds across the range of chemical sciences,our aim of this review is to provide a concise overview of recent advances of sulfonium salt and sulfur ylide chemistry.Selected examples are organized in three parts on the basis of their role in organic reactions(reactants,intermediates and catalysts).展开更多
A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis is disclosed, facilitating the construction of C-aryl/alkenyl glycals under mild conditions in high yields.T...A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis is disclosed, facilitating the construction of C-aryl/alkenyl glycals under mild conditions in high yields.The protocol tolerates a wide scope of functional groups including ketone, cyano, ester, amide, nitro,halide. The one-pot formal C–H glycosylation starting from arene is demonstrated with a reaction sequence of dibenzothiophenylation/Stille coupling. Besides, a gram-scale reaction is performed successfully,showing the high applicability of this protocol.展开更多
Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the p...Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the presence of polyphosphoric acid which can be used as dehydrate agent. The reaction condition was mild, such as reaction temperature between 40- 50 ℃ ,reactive time 2- 3 h, the yield of 4-（phenylthio）triphenylsulfonium hexafluorophosphate was 87.6%. The three kind sulfonium salts show better curing character to epoxy resin.展开更多
A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a ca...A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a cascade process including cross-coupling of the two reactants,[3,3]-sulfonium rearrangement,and 5-exo-dig heterocyclization,leading to tetrasubstituted furan products.The resultant α-alkylthio groups can be used for further functionalization,such as to introduce other alkyl/aryl groups.展开更多
The modification and functionalization of peptides is of great significance in modern biotechnology and drug development. Here we report a highly reactive Michael-type warhead for the covalently modification of cystei...The modification and functionalization of peptides is of great significance in modern biotechnology and drug development. Here we report a highly reactive Michael-type warhead for the covalently modification of cysteine on peptide and protein. By installing a vinyl group onto a methionine residue of peptide,the produced vinyl sulfonium can be efficiently nucleophilic added by appropriate cysteine residue of this peptide, and thus yield a cyclized peptide. This peptide cyclization strategy was proven to exhibit improved cell penetration and good stability. Moreover, a peptide ligand bearing vinyl sulfonium could covalently bind to the cysteine in the target protein, indicating the potential of vinyl sulfonium as a novel warhead for developing covalent peptide inhibitor.展开更多
A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under ac...A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under acidic conditions,sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations.While under alkaline conditions,cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently.The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.展开更多
Whilst most bioorthogonal reactions focus on targeting binding-site cysteine residues,proximity-induced reactivity effect ensures that reaction also occurs at nucleophilic lysine residues.We report one example here th...Whilst most bioorthogonal reactions focus on targeting binding-site cysteine residues,proximity-induced reactivity effect ensures that reaction also occurs at nucleophilic lysine residues.We report one example here that the propargylated-sulfonium center undergoes a nucleophilic reaction with lysine residue via proximity-induced conjugation.This propargylated-sulfonium tethered peptide resulting from a facile propargylation of thiolethers,enables amino-yne reaction at the selected lysine on MDM4 protein.This strategy represents a viable approach of lysine-targeted covalent inhibition in proximity.展开更多
A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The form...A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.展开更多
Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(...Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.展开更多
Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reacti...Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reaction conditions,and good functional group compatibility,offering a straightforward and efficient preparation route for terminal vinyl phosphine oxides.展开更多
A chirality induced helicity method has been developed to modulate the peptide＇s biophysical and biochemical properties. We report herein a novel approach for reversibly switching the conformation of short constraint...A chirality induced helicity method has been developed to modulate the peptide＇s biophysical and biochemical properties. We report herein a novel approach for reversibly switching the conformation of short constraint a-helical peptides through alkylation of the in-tether thioether and dealkylation of the chiral sulfonium. This traceless redox sensitive tagging strategy broadened our scope of CIH （chirality induced helicity） strategy and provided a valuable approach to functionalize the peptide tether.展开更多
The development of a series of shelf-stable monofluoroalkylated sulfonium ylide reagents and their reactions with a variety of O-nucleophiles including phenols,sulfonic acids,carboxylic acids,1-hydroxy-benzotrizoles,a...The development of a series of shelf-stable monofluoroalkylated sulfonium ylide reagents and their reactions with a variety of O-nucleophiles including phenols,sulfonic acids,carboxylic acids,1-hydroxy-benzotrizoles,amino acids was described.In general,monofluoroakylated sulfonium ylides were synthesized in three steps from commercially available starting materials including thiophenols,alkyl halides and dimethyl 2-diazomalonate.Reactions with the O-nucleophiles occurred under mild conditions and afforded the corresponding monofluoroalkylated ethers,sulfonates,and esters in good to excellent yields,thus providing a robust approach for the preparation of these compounds.Further expansion of monofluoroalkylation of C-terminus of peptides potentially provided modifieddrug-like peptides.展开更多
The development of a nucleophilic fluorination protocol using hydrofluoric acid as the fluoride source represents a long-sought goal in the field of organofluorine chemistry.We report herein the realization of such a ...The development of a nucleophilic fluorination protocol using hydrofluoric acid as the fluoride source represents a long-sought goal in the field of organofluorine chemistry.We report herein the realization of such a reaction that employed alkyl-substituted sulfonium ylides as the substrates.The key to the success of the protocol was attributed to two factors:First,as a Brϕnsted base,the ylide was able to be protonated by HFaq,thus serving as a phase-transfer shuttle generated in situ to bring F−from aqueous phase to the organic phase promoting desolvation of fluoride ion.Second,after protonation,a sulfonium salt,a good leaving group,was generated and subsequent attacked by the fluoride to afford the alkyl fluoride.Mechanistic investigation indicates that the reaction occurs via an SN1 pathway.Because of the nature of the cationic intermediate in the reaction,two attractive rearrangement-fluorination approaches including 1,2-aryl migration fluorination and ring-expansion fluorination were disclosed.展开更多
基金financial support by the National Natural Science Foundation of China(Nos.22301107,52373057)Nature Science Foundation of Jiangsu Province(No.BK20242080)+1 种基金Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,Jiangnan University(No.1042050205243170/008)State Key Laboratory of Molecular Engineering of Polymers,Fudan University(No.K2024-39).
文摘Developing high-efficient,multi spectral applicable one-component macrophotoinitiators(Macro-PIs)with excellent performance that can simultaneously initiate cationic polymerization(CP),free radical polymerization(FRP),and hybrid polymerization(HP)has been a charming research direction.Herein,we synthesized a novel cationic macro-PI(P-CSS)by copolymerizing polymerizable coumarin sulfonium salt(CSS)and methyl methacrylate(MMA).Photochemical and photophysical investigations indicated that the extraordinary absorption ability and the 50 nm redshift of P-CSS may be due to chromophores aggregating on the side chain.Photopolymerization kinetics studies established that P-CSS has effective initiating ability for FRP and CP both under LED@365,405 nm and under Laser@980 nm(with upconversion particles,UCPs).The migration stability experiments showed that the migration rate of P-CSS in trimethylolpropane triacrylate(TMTPA)polymer is 1.25%of CSS,and in 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate(EPOX)polymer is 1.96%.These results indicate the great potential of P-CSS in preparing biosafety and environmentally friendly polymers for packaging and biological materials.
文摘Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.
基金supported by the Science and Technology Foundation of Shenzhen, Shenzhen Science and Technology Innovation Committee (No. JCYJ20170818143001461)
文摘A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described.And a broad range of difluoromthyl enol ethers were readily accessed in good to excellent yields under mild reaction conditions.Mechanistic studies revealed that the O-difluoromethylation reaction proceeds mainly via a difluorocarbene pathway.
文摘Two electrophilic pentafluoroethylating reagents of pentafluoroethyl(p-methylphenyl)sulfonium bis(carbometh-oxy)methylide(4a)and pentafluoroethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide(4b),and their reactions under mild conditions withβ-ketoesters,aryl iodides and heteroaromatics are described.
基金financially supported by the National Natural Science Foundation of China(Nos.51173134 and 51573139)Fundamental Research Funds for the Central Universities and the Open Measuring Fund for Large Instrument and Equipment(No.0002015033)of Tongji University
文摘A series of D-π-A type sulfonium salt photoacid generators with different π-conjugated structures, such as triphenyl, phenylstilbene, styryl-biphenyl, and stilbene, were designed to determine the effect of molecular structures on the photochemical and photophysical properties. The mechanisms of photochemical generation of H＋ were studied by UV-Vis spectroscopy, theoretical calculations, and fluorescence spectroscopy. It is found that the frontier orbits determine the absorption, the molar extinction coefficients, and the quantum yields of photoacid generation. Triphenyl systems connected with sulfonium are beneficial to increase the quantum yields of acid generation. The photoreactivity of four sulfonium salts was further evaluated through the polymerizations of various epoxide monomers at different irradiation wavelengths （365- 425 nm） by using the real-time infrared spectroscopy with light-emitting diodes. The high quantum yields for acid generation （ФH＋ = -0.32 to 0.58） and the high molar extinction coefficients （ε = -23500 L.mol-1.cm-1 to 31000 L.mol-1.cm-1） of the sulfonium salts lead to high conversion rates （over 50%-80%）. Hence, these photoinitiators exhibit potential for the photocuring applications.
基金Supported by the National Key R&D Program of China(No.2019YFD0900705)the Key Deployment Projects of the Marine Science Research Center of the Chinese Academy of Sciences(No.COMS2020J04)the Natural Science Foundation of Shandong Province of China(No.ZR2019BD064)。
文摘To improve the solubility and bioactivity of chitosan,a new class of carboxymethyl chitosan derivatives possessing sulfonium salts was successfully designed and synthesized,including Methyl sulfi de carboxymethyl chitosan(MCMCS),Ethyl sulfi de carboxymethyl chitosan(ECMCS),Propyl sulfi de carboxymethyl chitosan(PCMCS),and Butyl sulfi de carboxymethyl chitosan(BCMCS).To determine the structure of the new class of the derivatives,methods of the Fourier transform infrared spectroscopy(FT-IR),^(1)H nuclear magnetic resonance spectrometer(^(1)H NMR),and^(13)C nuclear magnetic resonance spectrometer(^(13)C NMR)were used.Moreover,the antioxidant activity of the derivatives for three types of free radicals,i.e.,hydroxyl radical,superoxide radical,and 1,1-diphenyl-2-picrylhydrazyl(DPPH)radical was evaluated in vitro.In addition,the L929 cells were adopted to test the cytotoxicity of chitosan and its derivatives by CCK-8 assay.The class of the carboxymethyl chitosan derivatives showed a strong scavenging ability against the three free radicals at 1.6 mg/mL,with scavenging rate of over 70%and some up to 100%.At this high rate,the overall cell viability in the toxicity test reached more than 80%,indicating that the synthetic derivative had a little cytotoxicity.The results show that the introduction of carboxymethyl group to chitosan increased the water-solubility of chitosan,and the combination of sulfonate ions with diff erent chain lengths further enhanced the antioxidant activity of chitosan.Therefore,the sulfonium-containing carboxymethyl chitosan derivatives had excellent bioactivity with good application prospects in food,biomedicine,and medical fi elds.
基金This work was partially supported by a Grant-in-Aid for Research Fellow of the Japan Society for the Promotion of Science(No.085410)and International Scientific Research(Joint Research No.08044174)from the Ministry of Education,Science,Sports and Culture
文摘The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in an acidic solution under atmosphericconditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acety-lacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen ox-idative polymerization. The polymerization mechanism involves multielectron oxidation ofthe sulfides followed by successive electrophilic substitution. The resulting polyarylenesul-fonium cations are useful as a soluble precursor for the synthesis of high molecular weight(M_w>10~5) poly(thio arylne)s.
基金the support from the National Natural Science Foundation of China(No.21702013)the Fundamental Research Funds for the Central Universities(Nos.XK1802-6 and buctrc201721)at the BUCT.JTan and Y.Liu are thankful for the support from the Open Project Program(No.SPFW2019YB06)of Beijing Key Laboratory of Flavor Chemistry,Beijing Technology and Business University(BTBU)。
文摘Sulfonium salts and sulfur ylides are important S(Ⅳ) motifs,and have displayed many unique reactivities to provide simple,effective,and often stereoselective synthesis toward sulfur containing compounds.Impressive developments have been witnessed within this field during the past several years.In light of the increasing demand of organosulfur compounds across the range of chemical sciences,our aim of this review is to provide a concise overview of recent advances of sulfonium salt and sulfur ylide chemistry.Selected examples are organized in three parts on the basis of their role in organic reactions(reactants,intermediates and catalysts).
基金Fuzhou University (No. 511041)the Fujian Provincial Department of Education (No. 602512) for financial support。
文摘A highly efficient coupling of glycosyl stannanes and sulfonium salts enabled by synergistic Pd/Cu catalysis is disclosed, facilitating the construction of C-aryl/alkenyl glycals under mild conditions in high yields.The protocol tolerates a wide scope of functional groups including ketone, cyano, ester, amide, nitro,halide. The one-pot formal C–H glycosylation starting from arene is demonstrated with a reaction sequence of dibenzothiophenylation/Stille coupling. Besides, a gram-scale reaction is performed successfully,showing the high applicability of this protocol.
文摘Three kind of aryl-substituted tri-benzyl sulfonium salts [ （4-phX）phSph2 ] PF6 [ X = S, O ] were prepared by the condensation of biphenyl sulfoxide with biphenyl sulfide, biphenyl ether or 1, 1＇ -biphenyl in the presence of polyphosphoric acid which can be used as dehydrate agent. The reaction condition was mild, such as reaction temperature between 40- 50 ℃ ,reactive time 2- 3 h, the yield of 4-（phenylthio）triphenylsulfonium hexafluorophosphate was 87.6%. The three kind sulfonium salts show better curing character to epoxy resin.
文摘A transition-metal-free strategy for the synthesis of tetrasubstituted furans is reported.Promoted by boron trifluo-ride diethyl etherate,the reaction of alkynyl sulfoxides with ynamides/ynol ethers proceeded via a cascade process including cross-coupling of the two reactants,[3,3]-sulfonium rearrangement,and 5-exo-dig heterocyclization,leading to tetrasubstituted furan products.The resultant α-alkylthio groups can be used for further functionalization,such as to introduce other alkyl/aryl groups.
基金financial support from the National Key Research and Development Program"Synthetic Biology"Key Special Project of China (No. 2018YFA0902504)the China Postdoctoral Science Foundation (No. 2021M690220)+7 种基金the National Natural Science Foundation of China (Nos. 21778009 and21977010)the Natural Science Foundation of Guangdong Province(Nos. 2019A1515110487, 2020A1515010522 and 2019A1515111184)the Shenzhen Science and Technology Innovation Committee (Nos. JCYJ20180507181527112, JCYJ20180508152213145, and JCYJ20170817172023838)the Foundation for Basic and Applied Research of Guangdong Province (No. 2019A1515110489)Guangdong Medical Science Foundation (No. A2021413)financial support from Beijing National Laboratory of Molecular Science Open Grant (No. BNLMS20160112)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions (No. 2019SHIBS0004)supported by the high-performance computing platform of Peking University。
文摘The modification and functionalization of peptides is of great significance in modern biotechnology and drug development. Here we report a highly reactive Michael-type warhead for the covalently modification of cysteine on peptide and protein. By installing a vinyl group onto a methionine residue of peptide,the produced vinyl sulfonium can be efficiently nucleophilic added by appropriate cysteine residue of this peptide, and thus yield a cyclized peptide. This peptide cyclization strategy was proven to exhibit improved cell penetration and good stability. Moreover, a peptide ligand bearing vinyl sulfonium could covalently bind to the cysteine in the target protein, indicating the potential of vinyl sulfonium as a novel warhead for developing covalent peptide inhibitor.
基金Financial support from National Natural Science Foundation of China(Nos.21877043,21702068,21772050,22025102)the Fundamental Research Funds for the Central Universities,HUST(Nos.2019kfyXKJC080,2019JYCXJJ046)Huazhong University of Science and Technology are greatly appreciated。
文摘A sulfonium ylide participated alkylation and arylation under transition-metal free conditions is described.The disparate reaction pattern allowed the separate activation of non-ylidic S-alkyl and S-aryl bond.Under acidic conditions,sulfonium ylides serve as alkyl cation precursors which facilitate the alkylations.While under alkaline conditions,cleavage of non-ylidic S-aryl bond produces O-arylated compounds efficiently.The robustness of the protocols were established by the excellent compatibility of wide variety of substrates including carbohydrates.
基金financial support from the National Key Research and Development Program"Synthetic Biology"Key Special Project of China(No.2018YFA0902504)the Natural Science Foundation of China(Nos.21778009 and 21977010)+6 种基金the Natural Science Foundation ofGuangdongProvince(Nos.2020A1515010766,2020A1515010522,2019A1515111184 and 2019A1515110489)the Shenzhen Science and Technology Innovation Committee(Nos.JCYJ20180507181527112,JCYJ20180508152213145,and JCYJ20170817172023838)financial support from Beijing National Laboratory of Molecular Science Open Grant(No.BNLMS20160112)Shenzhen-Hong Kong Institute of Brain Science-Shenzhen Fundamental Research Institutions(No.2019SHIBS0004)supported by Proteomic Platform of Pingshan Translational Medicine CenterShenzhen Bay Laboratorythe high-performance computing platform of Peking University.
文摘Whilst most bioorthogonal reactions focus on targeting binding-site cysteine residues,proximity-induced reactivity effect ensures that reaction also occurs at nucleophilic lysine residues.We report one example here that the propargylated-sulfonium center undergoes a nucleophilic reaction with lysine residue via proximity-induced conjugation.This propargylated-sulfonium tethered peptide resulting from a facile propargylation of thiolethers,enables amino-yne reaction at the selected lysine on MDM4 protein.This strategy represents a viable approach of lysine-targeted covalent inhibition in proximity.
基金supported by National Natural Science Foundation of China(Nos.21702153 and 21801194).
文摘A stimuli-responsive supramolecular polymer network has been constructed based on the host-vip interactions between the copolymer poly-P[5]A with pendent pillararene units and bis(sulfonium)diction vip G2.The formation mechanism of the supramolecular polymer network has been explored by the intensive study.With the addition of the competitive molecules and heating,the supramolecular polymer network could be dissociated and lead to clear changes in NMR spectroscopy and viscosity property.
基金supported by the National Natural Science Foundation of China(No.22271170)the Scientific Research Foundation of Qingdao University of Science and Technology。
文摘Developing applicable methods to forge linkages between sp^(3)and sp^(2)-hydridized carbons is of great significance in drug discovery.We show here a new,Ni-catalyzed reductive cross-coupling reaction that forms Csp^(3)-Csp^(2)bonds from aryl iodides and cyclic sulfonium salts.Notably,Csp^(3)-Csp^(2)bonds can be forged selectively at the iodine-bearing carbon of bromo(iodo)arenes which is usually recognized as a huge challenge under the catalytic reductive cross-coupling(CRCC)conditions.Experimental and computational mechanistic studies support LNi~IAr as an active species,while the untraditional anti-Markovnikov selective alkylation of asymmetric sulfonium salts is determined by the oxidative S-substitution of sulfonium salts with LNi~IAr.This protocol further expands the range of alkyl electrophiles under the CRCC conditions and provides a new strategy for the construction of Csp^(3)-Csp^(2)bonds.
文摘Cesium carbonate was used as a base to achieve the desulfurization reaction of alkenyl sulfonium salts and phosphine oxides at room temperature,forming C(sp2)—P bonds.This method features simple operation,mild reaction conditions,and good functional group compatibility,offering a straightforward and efficient preparation route for terminal vinyl phosphine oxides.
基金financial support from the National Natural Science Foundation of China(Nos. 21372023 and 81572198)Ministry of Science and Technology of the People's Republic of China(No. 2015DFA31590)+1 种基金the Shenzhen Science and Technology Innovation Committee(Nos. JSGG20140519105550503, JCYJ20150331100849958,JCYJ20150403101146313, JCYJ20160301111338144,JCYJ20160331115853521, JSGG20160301095829250 and ZDSYS201504301539161)the Shenzhen Peacock Program(No. KQTD201103)
文摘A chirality induced helicity method has been developed to modulate the peptide＇s biophysical and biochemical properties. We report herein a novel approach for reversibly switching the conformation of short constraint a-helical peptides through alkylation of the in-tether thioether and dealkylation of the chiral sulfonium. This traceless redox sensitive tagging strategy broadened our scope of CIH （chirality induced helicity） strategy and provided a valuable approach to functionalize the peptide tether.
基金support from the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)for financial support.
文摘The development of a series of shelf-stable monofluoroalkylated sulfonium ylide reagents and their reactions with a variety of O-nucleophiles including phenols,sulfonic acids,carboxylic acids,1-hydroxy-benzotrizoles,amino acids was described.In general,monofluoroakylated sulfonium ylides were synthesized in three steps from commercially available starting materials including thiophenols,alkyl halides and dimethyl 2-diazomalonate.Reactions with the O-nucleophiles occurred under mild conditions and afforded the corresponding monofluoroalkylated ethers,sulfonates,and esters in good to excellent yields,thus providing a robust approach for the preparation of these compounds.Further expansion of monofluoroalkylation of C-terminus of peptides potentially provided modifieddrug-like peptides.
基金supported by the National Key Research and Development Program of China(Grant Number 2021YFF0701-700)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000).
文摘The development of a nucleophilic fluorination protocol using hydrofluoric acid as the fluoride source represents a long-sought goal in the field of organofluorine chemistry.We report herein the realization of such a reaction that employed alkyl-substituted sulfonium ylides as the substrates.The key to the success of the protocol was attributed to two factors:First,as a Brϕnsted base,the ylide was able to be protonated by HFaq,thus serving as a phase-transfer shuttle generated in situ to bring F−from aqueous phase to the organic phase promoting desolvation of fluoride ion.Second,after protonation,a sulfonium salt,a good leaving group,was generated and subsequent attacked by the fluoride to afford the alkyl fluoride.Mechanistic investigation indicates that the reaction occurs via an SN1 pathway.Because of the nature of the cationic intermediate in the reaction,two attractive rearrangement-fluorination approaches including 1,2-aryl migration fluorination and ring-expansion fluorination were disclosed.
