The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic comp...The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.展开更多
Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangemen...Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangement reaction, which can simultaneously construct C–C bonds and C–X(X = S/Se) bonds using sulfoxonium ylides as starting materials to obtain sulfur-or selenium-containing compounds. This strategy is characterized by the safer and greener carbene precursor, high yields and broad substrate scope, possessing a wide range of application.展开更多
A simple and additive-free protocol has been developed for the preparation ofβ-keto phosphorodithioates through the three-component reaction of easily available sulfoxonium ylides,P_(4)S_(10),and alcohols.The present...A simple and additive-free protocol has been developed for the preparation ofβ-keto phosphorodithioates through the three-component reaction of easily available sulfoxonium ylides,P_(4)S_(10),and alcohols.The present geminal hydro-phosphorodithiolation reaction was performed at room temperature to construct a series ofβ-keto phosphorodithioates in the absence of any metal reagents,bases,or additives.展开更多
facile one-step method is presented for the synthesis of indolizines in moder-ate to high yields by reaction of pyridinium, quinolinium and isoquinolinium ylideswith acrylonitrile, methyl acrylate and diethyl maleate ...facile one-step method is presented for the synthesis of indolizines in moder-ate to high yields by reaction of pyridinium, quinolinium and isoquinolinium ylideswith acrylonitrile, methyl acrylate and diethyl maleate respectively in the presenceof tetrakis-pyridino-cobalt(Ⅱ)dichromate (TPCD) in DMF.展开更多
Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselec...Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselectivity,providing a facile and efficient approach to access a variety of 2-aminothiazole derivatives with good functional groups tolerance.展开更多
Disclosed herein is an efficient Ag-catalyzed 4+1 heteroannulation reaction of enamides withα-carbonyl sulfoxonium ylides.The diastereoselective transformation provides a practical access to a diverse range of multi-...Disclosed herein is an efficient Ag-catalyzed 4+1 heteroannulation reaction of enamides withα-carbonyl sulfoxonium ylides.The diastereoselective transformation provides a practical access to a diverse range of multi-functionalized oxazoline derivatives.The synthetic utility of the resultant tetrasubstituted oxazolines is further demonstrated by a series of useful manipulations into valuable building blocks of pharmaceutical relevance.展开更多
Cu-catalyzed endo-selective asymmetric 1,3-dipolar cycloaddition of azomethine ylides with ethenesulfonyl fluorides(ESFs) was successfully developed, this protocol provided an efficient and facile method to a wide ran...Cu-catalyzed endo-selective asymmetric 1,3-dipolar cycloaddition of azomethine ylides with ethenesulfonyl fluorides(ESFs) was successfully developed, this protocol provided an efficient and facile method to a wide range of chiral pyrrolidine-3-sulfonyl fluorides with good to excellent results(up to 87% yield,>20:1 dr, 94% ee). Some other chiral sulfonyl derivatives, such as sulfonamide and sulfonate, were easily accessible through simple transformations with high yields, which demonstrated that the cycloaddition products could be synthetically useful in the sulfur(VI) fluoride exchange(Su FEx) chemistry.展开更多
A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free condi...A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free conditions and tolerates various functional groups.Starting from diverse readily available sulfoxonium ylides and dioxazolones,a variety of benzoxazinones could be synthesized in one step in 32%-75%yields.展开更多
An efficient synthesis of 6-arylindazolo[2,3-a]quinolines starting from 2-aryl-2H-indazoles with sulfoxonium ylides via rhodium(Ⅲ)-catalyzed C-H activation and cyclization reaction has been described.This transformat...An efficient synthesis of 6-arylindazolo[2,3-a]quinolines starting from 2-aryl-2H-indazoles with sulfoxonium ylides via rhodium(Ⅲ)-catalyzed C-H activation and cyclization reaction has been described.This transformation features high efficiency,tolerates various functional groups,avoids external oxidant and produces dimethyl sulfoxide(DMSO)and H2O as the sole by-products.In addition,the scale-up reaction demonstrated the practicability of this protocol in industry.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
Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides....Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.展开更多
α-Seleno arsonium ylides 5 have been synthesized through the reaetion of α- unfunctionalized arsonium ylides 4 with almost equimolar phenylselenenyl iodide 2.
We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with m...We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with methyl 2-perfluoroalkynoates(2).展开更多
The deoxygenation reaction of heptanones, cycloheptanone, cycloheptatrienone or substituted cycloheptatrienone with dihalo-carbene results in carbon monoxide and corresponding halides. The yield of CO produced by 2 , ...The deoxygenation reaction of heptanones, cycloheptanone, cycloheptatrienone or substituted cycloheptatrienone with dihalo-carbene results in carbon monoxide and corresponding halides. The yield of CO produced by 2 , 4 , 6-triphenylcycloheptatrienone is 2.6-3.5 times as high as that produced by the saturated heptanones. The structures, energies, charge distributions, bond orders, and other relative parameters of the dihalocarbonyl glides were calculated by using the SCF-MNDO method. The obtained data reveal that the ylides from cycloheptatrienone have aromatic structure and are different from those produced from saturated cycloheptanone. The reactivities of the dihalocarbonyl ylides are discussed. It is proposed that this aromatic structure should be responsible for the high yield of CO from the reaction of cycloheptatrienone with dihalocarbene.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
The asymmetric cycloaddition reactions of 1,3-fused cyclic azomethine ylides have been extensively studied,but the non-cyclicα-functionalization of these compounds remains unexplored.Herein,an efficient combination o...The asymmetric cycloaddition reactions of 1,3-fused cyclic azomethine ylides have been extensively studied,but the non-cyclicα-functionalization of these compounds remains unexplored.Herein,an efficient combination of the catalytic enantioselective non-cyclicα-functionalization of 1,3-fused cyclic azomethine ylides and the remote-controlled asymmetric desymmetrization of N-arylmaleimides and cyclopentene-1,3-diones has been achieved with a catalyst system consisting of a chiral P,N-ferrocene ligand and AgNO2.This reaction allowed for the synthesis of a series of enantioenriched 3,4-dihydroisoquinoline derivatives bearing multiple stereogenic elements/centers with good yields and stereoselectivities.The practicality of this method was demonstrated by gram-scale synthesis and derivatizations of the products.展开更多
Herein,we report a novel and highly efficient method for the synthesis ofα-phosphoryloxy carbonyl compounds via Rucatalyzed P(O)O–H insertion reactions of sulfoxonium ylides and phosphinic acids,with the assistance ...Herein,we report a novel and highly efficient method for the synthesis ofα-phosphoryloxy carbonyl compounds via Rucatalyzed P(O)O–H insertion reactions of sulfoxonium ylides and phosphinic acids,with the assistance of high-throughput experimentation(HTE)and machine learning(ML).A variety of P(O)O−H derivatives,including diarylphosphates,alkyl phosphates,and alkoxyphosphates,are competent candidates to react with sulfoxonium ylides in this transformation,and variousα-phosphoryloxy carbonyls and propylene phosphates are directly constructed.This approach utilizes readily available sulfoxonium ylide as a carbene precursor,and features mild conditions,operational simplicity,and broad functional groups tolerance,and could be used for late-stage functionalization of structurally complex bioactive molecules.Moreover,a conducive exploration of the reaction space is also conducted(756 reactions)and a machine learning model for reaction yield prediction has been developed and applied,showcasing the practical application of this newly workflow(HTE-ML)in the field of synthetic chemistry.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
Enantioenrichedγ-butenolides constitute the structural core of many natural products and biologically active molecules,but their direct and atom-economical asymmetric assembly from simple starting materials remains q...Enantioenrichedγ-butenolides constitute the structural core of many natural products and biologically active molecules,but their direct and atom-economical asymmetric assembly from simple starting materials remains quite limited.Here,we describe a facile and atom-efficient synthesis of enantioenrichedα-aryl-γ-butenolides from cyclopropenyl carboxylic acid and electrondeficient olefins or isatins.The reaction proceeds via carboxylic acid insertion of carbenoid initiated by an achiral rhodium salt,followed by chiral Lewis acid-mediated enantioselective trapping of the resulting carboxylic oxonium ylides with enones and isatins.Various enantioenrichedγ-butenolides were obtained in high yields(up to 99%)with excellent stereoselectivities(up to>19:1 dr and up to 96%ee)under mild conditions by low catalyst loading(S/C=200).The potential application of these methods was demonstrated by the gram-scale synthesis ofγ-butenolides and their further transformations into other bioactive molecules.展开更多
Herein,organophotoredox-catalyzed annulation of enamines with sulfoxonium ylides to construct pyrrole derivatives is developed under transition-metal-free and mild condition.A broad range of readily accessible substra...Herein,organophotoredox-catalyzed annulation of enamines with sulfoxonium ylides to construct pyrrole derivatives is developed under transition-metal-free and mild condition.A broad range of readily accessible substrates are suitable for this protocol,providing a convenient and efficient approach to preparing pyrrole derivatives with satisfying yields.Mechanistically,a photoredox-mediated radical chain mechanistic pathway is proposed for this reaction by a synergistic experimental and computational study.Two key radicals,α-imino andα-carbonyl C-radicals derived from enamines and sulfoxonium ylides,respectively,could be generated via two steps of single-electron transfer in a photoredox catalytic loop.Subsequently,the formedα-carbonyl C-radical may attack the alkenyl moiety of enamines.Next,the formed radical adduct could undergo H-atom transfer with sulfoxonium ylides to regenerate the keyα-carbonyl C-radical and thus fulfill the chain propagation process.The afforded adduct intermediate could undergo an intramolecular cyclization followed by dehydration to furnish the desired pyrrole derivatives.展开更多
文摘The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.
基金supported by Sichuan Science and Technology Program (No.2020YJ0221)。
文摘Doyle-Kirmse rearrangement reactions have received continuous attention as an important method for constructing complex chemical structures. Herein, we disclosed an efficient rhodium-catalyzed DoyleKirmse rearrangement reaction, which can simultaneously construct C–C bonds and C–X(X = S/Se) bonds using sulfoxonium ylides as starting materials to obtain sulfur-or selenium-containing compounds. This strategy is characterized by the safer and greener carbene precursor, high yields and broad substrate scope, possessing a wide range of application.
基金supported by the Natural Science Foundation of Shandong Province(No.ZR2021MB065)Scientific Research Startup Foundation of Qufu Normal University and National Natural Science Foundation of China(No.22101237)。
文摘A simple and additive-free protocol has been developed for the preparation ofβ-keto phosphorodithioates through the three-component reaction of easily available sulfoxonium ylides,P_(4)S_(10),and alcohols.The present geminal hydro-phosphorodithiolation reaction was performed at room temperature to construct a series ofβ-keto phosphorodithioates in the absence of any metal reagents,bases,or additives.
文摘facile one-step method is presented for the synthesis of indolizines in moder-ate to high yields by reaction of pyridinium, quinolinium and isoquinolinium ylideswith acrylonitrile, methyl acrylate and diethyl maleate respectively in the presenceof tetrakis-pyridino-cobalt(Ⅱ)dichromate (TPCD) in DMF.
基金support from the National Natural Science Foundation of China (Nos.81373259 and 81573286)Sichuan Science and Technology Program (Nos.2020YJ0221 and 2018JY0537)。
文摘Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselectivity,providing a facile and efficient approach to access a variety of 2-aminothiazole derivatives with good functional groups tolerance.
基金the National Natural Science Foundation of China(No.21702106)the Natural Science Foundation of Jiangsu Province(No.BK20170967)the Start-up Grant from Nanjing Tech University(No.39839101)for financial support。
文摘Disclosed herein is an efficient Ag-catalyzed 4+1 heteroannulation reaction of enamides withα-carbonyl sulfoxonium ylides.The diastereoselective transformation provides a practical access to a diverse range of multi-functionalized oxazoline derivatives.The synthetic utility of the resultant tetrasubstituted oxazolines is further demonstrated by a series of useful manipulations into valuable building blocks of pharmaceutical relevance.
基金the financial support from the National Natural Science Foundation of China (Nos. 21772147, 22071186, 22071187)Natural Science Foundation of Hubei Province (No. 2020CFA036)+1 种基金Natural Science Foundation of Jiangsu Province (No. SKB2019041078)The Program of Introducing Talents of Discipline to Universities of China (111 Project) is also appreciated。
文摘Cu-catalyzed endo-selective asymmetric 1,3-dipolar cycloaddition of azomethine ylides with ethenesulfonyl fluorides(ESFs) was successfully developed, this protocol provided an efficient and facile method to a wide range of chiral pyrrolidine-3-sulfonyl fluorides with good to excellent results(up to 87% yield,>20:1 dr, 94% ee). Some other chiral sulfonyl derivatives, such as sulfonamide and sulfonate, were easily accessible through simple transformations with high yields, which demonstrated that the cycloaddition products could be synthetically useful in the sulfur(VI) fluoride exchange(Su FEx) chemistry.
基金financial support from the Hunan Provincial Innovation Foundation for Postgraduate(No.CX20190267)Natural Science Foundation of Hunan Province(No.2020JJ4171)。
文摘A highly novel and direct synthesis of benzoxazinones was developed via Cp*Co(Ⅲ)-catalyzed C-H activation and[3+3]annulation between sulfoxonium ylides and dioxazolones.The reaction is conducted under base-free conditions and tolerates various functional groups.Starting from diverse readily available sulfoxonium ylides and dioxazolones,a variety of benzoxazinones could be synthesized in one step in 32%-75%yields.
文摘An efficient synthesis of 6-arylindazolo[2,3-a]quinolines starting from 2-aryl-2H-indazoles with sulfoxonium ylides via rhodium(Ⅲ)-catalyzed C-H activation and cyclization reaction has been described.This transformation features high efficiency,tolerates various functional groups,avoids external oxidant and produces dimethyl sulfoxide(DMSO)and H2O as the sole by-products.In addition,the scale-up reaction demonstrated the practicability of this protocol in industry.
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partial financial support from the Ministry of Science and Technology of China (No. 2016YFE0132600)Zhengzhou University
文摘Rhodium(Ⅲ)-catalyzed synthesis of indole derivatives has been realized via cascade reaction of C -H alkylation/nucleophilic cyclization starting from readily available N-phenylpyridin-2-amines and sulfoxonium ylides. Notably, this transformation could smoothly proceed with high yields, good regioselectivity, and feature broad group tolerance and under redox-neutral condition to avoid external oxidant. The titled products are potentially important building blocks in the organic synthesis through various chemical transformations.
基金National Natural Science Foundation of China!29502006
文摘α-Seleno arsonium ylides 5 have been synthesized through the reaetion of α- unfunctionalized arsonium ylides 4 with almost equimolar phenylselenenyl iodide 2.
文摘We reported the stereoselectlve synthesis of fluorine-containing trisubstituted ethylenes(4) by hydrolysis of the adducts(3) which are the products of the reactions of some stable phosphonium or arsonium ylides with methyl 2-perfluoroalkynoates(2).
文摘The deoxygenation reaction of heptanones, cycloheptanone, cycloheptatrienone or substituted cycloheptatrienone with dihalo-carbene results in carbon monoxide and corresponding halides. The yield of CO produced by 2 , 4 , 6-triphenylcycloheptatrienone is 2.6-3.5 times as high as that produced by the saturated heptanones. The structures, energies, charge distributions, bond orders, and other relative parameters of the dihalocarbonyl glides were calculated by using the SCF-MNDO method. The obtained data reveal that the ylides from cycloheptatrienone have aromatic structure and are different from those produced from saturated cycloheptanone. The reactivities of the dihalocarbonyl ylides are discussed. It is proposed that this aromatic structure should be responsible for the high yield of CO from the reaction of cycloheptatrienone with dihalocarbene.
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the National Natural Science Foundation of China(Nos.22171029,22271027)Natural Science Foundation of Sichuan Province(2024NSFSC1115)Chemical Synthesis and PollutionControl KeyLaboratory of Sichuan Province(CSPC202406)for the financial support.
文摘The asymmetric cycloaddition reactions of 1,3-fused cyclic azomethine ylides have been extensively studied,but the non-cyclicα-functionalization of these compounds remains unexplored.Herein,an efficient combination of the catalytic enantioselective non-cyclicα-functionalization of 1,3-fused cyclic azomethine ylides and the remote-controlled asymmetric desymmetrization of N-arylmaleimides and cyclopentene-1,3-diones has been achieved with a catalyst system consisting of a chiral P,N-ferrocene ligand and AgNO2.This reaction allowed for the synthesis of a series of enantioenriched 3,4-dihydroisoquinoline derivatives bearing multiple stereogenic elements/centers with good yields and stereoselectivities.The practicality of this method was demonstrated by gram-scale synthesis and derivatizations of the products.
基金supported by the National Natural Science Foundation of China(22372044,22393892,22002169,22071249)the Guangdong Basic and Applied Basic Research Foundation(2024A1515012583,2019A1515111111)the Major Program of Guangzhou National Laboratory(GZNL2023A02012)。
文摘Herein,we report a novel and highly efficient method for the synthesis ofα-phosphoryloxy carbonyl compounds via Rucatalyzed P(O)O–H insertion reactions of sulfoxonium ylides and phosphinic acids,with the assistance of high-throughput experimentation(HTE)and machine learning(ML).A variety of P(O)O−H derivatives,including diarylphosphates,alkyl phosphates,and alkoxyphosphates,are competent candidates to react with sulfoxonium ylides in this transformation,and variousα-phosphoryloxy carbonyls and propylene phosphates are directly constructed.This approach utilizes readily available sulfoxonium ylide as a carbene precursor,and features mild conditions,operational simplicity,and broad functional groups tolerance,and could be used for late-stage functionalization of structurally complex bioactive molecules.Moreover,a conducive exploration of the reaction space is also conducted(756 reactions)and a machine learning model for reaction yield prediction has been developed and applied,showcasing the practical application of this newly workflow(HTE-ML)in the field of synthetic chemistry.
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 R&D Program of China(2023YFA1506700)the National Natural Science Foundation of China(22271199,92256303)+1 种基金the Sichuan Science and Technology Program(2023YFSY0063)the Sichuan University(2020SCUNL204)。
文摘Enantioenrichedγ-butenolides constitute the structural core of many natural products and biologically active molecules,but their direct and atom-economical asymmetric assembly from simple starting materials remains quite limited.Here,we describe a facile and atom-efficient synthesis of enantioenrichedα-aryl-γ-butenolides from cyclopropenyl carboxylic acid and electrondeficient olefins or isatins.The reaction proceeds via carboxylic acid insertion of carbenoid initiated by an achiral rhodium salt,followed by chiral Lewis acid-mediated enantioselective trapping of the resulting carboxylic oxonium ylides with enones and isatins.Various enantioenrichedγ-butenolides were obtained in high yields(up to 99%)with excellent stereoselectivities(up to>19:1 dr and up to 96%ee)under mild conditions by low catalyst loading(S/C=200).The potential application of these methods was demonstrated by the gram-scale synthesis ofγ-butenolides and their further transformations into other bioactive molecules.
基金the National Natural Science Foundation of China(22373073)the project of scientific and technologic infrastructure of Suzhou(SZS201708)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)for financial support.
文摘Herein,organophotoredox-catalyzed annulation of enamines with sulfoxonium ylides to construct pyrrole derivatives is developed under transition-metal-free and mild condition.A broad range of readily accessible substrates are suitable for this protocol,providing a convenient and efficient approach to preparing pyrrole derivatives with satisfying yields.Mechanistically,a photoredox-mediated radical chain mechanistic pathway is proposed for this reaction by a synergistic experimental and computational study.Two key radicals,α-imino andα-carbonyl C-radicals derived from enamines and sulfoxonium ylides,respectively,could be generated via two steps of single-electron transfer in a photoredox catalytic loop.Subsequently,the formedα-carbonyl C-radical may attack the alkenyl moiety of enamines.Next,the formed radical adduct could undergo H-atom transfer with sulfoxonium ylides to regenerate the keyα-carbonyl C-radical and thus fulfill the chain propagation process.The afforded adduct intermediate could undergo an intramolecular cyclization followed by dehydration to furnish the desired pyrrole derivatives.
