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
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 new family of dibenzoullazine derivatives was synthesized through 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with alkynylbenziodoxoles followed by oxidation.The benziodoxole moiety in the res...A new family of dibenzoullazine derivatives was synthesized through 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with alkynylbenziodoxoles followed by oxidation.The benziodoxole moiety in the resulting products was used as a versatile linchpin for the synthesis of structurally diverse functional dibenzoullazines that are difficult to access by other synthetic methods.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 thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethy...A thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethyl-4-aminoquinolines in high yields.The reaction proceeds smoothly with or without the addition of sulfur and utilizes difluorocarbene as a C1 synthon under simply heating conditions.Mechanistic study reveals that in-situ generated thiocarbonyl fluoride,isothiocyanate or gem-difluoroalkene might act as the key reaction intermediates.展开更多
Azomethine ylides are useful intermediates for the rapid construction of chiral N-containing compounds.However,its synthetic potential has not been fully developed due to the limited reaction models.In combination wit...Azomethine ylides are useful intermediates for the rapid construction of chiral N-containing compounds.However,its synthetic potential has not been fully developed due to the limited reaction models.In combination with synergistic catalysis and azomethine ylide chemistry,we have developed several types of novel catalytic system including Cu/Pd,Cu/Ir and PTC/Ir catalysis;which can convert readily-available azomethine ylides to various high-valued molecules such as unnatural a-amino acids,homoallylic amines and N-heterocycles.Compared with the traditional mono-catalysis,the synergistic catalyst system exhibits enhanced catalytic efficiency and chiral induction ability in many cases.In addition,we have demonstrated that these strategies could be applied in the construction of bioactive compounds and natural products.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
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
A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation...A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives,affording the corresponding sulfoxonium ylides in moderate to good yields.The success of late-stage modification of natural isolates or drug candidates,scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.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
The introduction of a trifluoromethanesulfenyl group(SCF3)into organic molecules can,in principle,significantly enhance the cell-membrane permeability,metabolic stability and bioavailability because of its high lipoph...The introduction of a trifluoromethanesulfenyl group(SCF3)into organic molecules can,in principle,significantly enhance the cell-membrane permeability,metabolic stability and bioavailability because of its high lipophilicity and intrinsic electron-withdrawing properties.As a consequence,tremendous efforts have been made to develop diverse trifluoromethylthiolation protocols by using either展开更多
Enantioenrichedγ-butenolides are valuable structural cores in many pharmaceuticals and natural products,but their direct and catalytically asymmetric assembly remains rare.Here,we report an efficient,atom-economic sy...Enantioenrichedγ-butenolides are valuable structural cores in many pharmaceuticals and natural products,but their direct and catalytically asymmetric assembly remains rare.Here,we report an efficient,atom-economic synthetic strategy for enantioenrichedγ-butenolides via a unique enantioselective reaction of cyclopropene carboxylic acids with imines under the synergistic catalysis of Rh2(esp)2/chiral Brønsted acid system.The reaction involved trapping of carboxylic oxonium ylides,generated from cyclopropene carboxylic acids,which presented as the first asymmetric trapping reactive intermediate in the process.展开更多
An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out unde...An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out under transition-metal-free conditions.A broad range of functional groups were tolerant under mild conditions,and a variety of 2-pyrones were obtained in moderate to good yields.展开更多
The title compounds 6a—6f were prepared with high yield via intramolecular Wittig reaction of methyl 3-perfluoroalkyl-6-perfluoroacyl-2-triphenylphosphoranylidenehex-3,5-dienoates (5a—5i)which were obtained from the...The title compounds 6a—6f were prepared with high yield via intramolecular Wittig reaction of methyl 3-perfluoroalkyl-6-perfluoroacyl-2-triphenylphosphoranylidenehex-3,5-dienoates (5a—5i)which were obtained from the reaciton of 3-perfluoroacylprop-2-enylidenetriphenylphos- phoranes(3a—3c)with methyl perfluoroalkynoates(4a—4c).展开更多
Asymmetric 1,3-dipolar cycloaddition of methyl a-fluoroacrylate with azomethine ylides for the construction of optically active fluorinated pyrrolidines bearing one unique fluorinated quaternary and two tertiary stere...Asymmetric 1,3-dipolar cycloaddition of methyl a-fluoroacrylate with azomethine ylides for the construction of optically active fluorinated pyrrolidines bearing one unique fluorinated quaternary and two tertiary stereogenic cen- ters has been achieved with Cu(CH3CN)4BF4/TF-BiphamPhos complexes for the first time. This catalytic system performs well over a broad scope of substrates, providing the synthetically useful adducts in good yields and excel- lent diastereoselectivities and good to high enantioselectivities.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
The first investigation on catalytic asymmetric [2,3]-sigmatrop-ic rearrangement of sulfur ylides generated from carbenoids and allenic phenyl sulfide was carried out. Up to 55% ee value was obtained.
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supported by Nanyang Technological University and the Agency for Science,Technology and Research(A*STAR)AME IRG grant(A2083c0056(SI)).
文摘A new family of dibenzoullazine derivatives was synthesized through 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with alkynylbenziodoxoles followed by oxidation.The benziodoxole moiety in the resulting products was used as a versatile linchpin for the synthesis of structurally diverse functional dibenzoullazines that are difficult to access by other synthetic methods.
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financial support from K.C.Wong Education Foundation(GJTD-2020-08).
文摘A thermally-induced multi-component reaction of CF_(3)-substituted imidoyl sulfoxonium ylides(TFISYs),amines and(triphenylphosphonio)difluoroacetate(PDFA)has been developed,allowing a facile access to 2-trifluoromethyl-4-aminoquinolines in high yields.The reaction proceeds smoothly with or without the addition of sulfur and utilizes difluorocarbene as a C1 synthon under simply heating conditions.Mechanistic study reveals that in-situ generated thiocarbonyl fluoride,isothiocyanate or gem-difluoroalkene might act as the key reaction intermediates.
基金C.J.W.thanks the NSFC(Grants 21772147,21525207,21372180,21172176,20972117,20702039)for financial supportthe Program of Introducing Talents of Discipline to Universities of China(111 Project)is also appreciated.
文摘Azomethine ylides are useful intermediates for the rapid construction of chiral N-containing compounds.However,its synthetic potential has not been fully developed due to the limited reaction models.In combination with synergistic catalysis and azomethine ylide chemistry,we have developed several types of novel catalytic system including Cu/Pd,Cu/Ir and PTC/Ir catalysis;which can convert readily-available azomethine ylides to various high-valued molecules such as unnatural a-amino acids,homoallylic amines and N-heterocycles.Compared with the traditional mono-catalysis,the synergistic catalyst system exhibits enhanced catalytic efficiency and chiral induction ability in many cases.In addition,we have demonstrated that these strategies could be applied in the construction of bioactive compounds and natural products.
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.
基金the National Natural Science Foundation of China(Nos.21971001 and 21702001)the Natural Science Foundation of Anhui Province(No.1808085MB47)the Open Fund for Discipline Construction,Institute of Physical Science and Information Technology,Anhui University,and the Start-Up Grant from Anhui University for financial support of this work.
文摘A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported.The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives,affording the corresponding sulfoxonium ylides in moderate to good yields.The success of late-stage modification of natural isolates or drug candidates,scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
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.
文摘The introduction of a trifluoromethanesulfenyl group(SCF3)into organic molecules can,in principle,significantly enhance the cell-membrane permeability,metabolic stability and bioavailability because of its high lipophilicity and intrinsic electron-withdrawing properties.As a consequence,tremendous efforts have been made to develop diverse trifluoromethylthiolation protocols by using either
基金supported by National Natural Science Foundation of China(no.21901259)Guangdong Basic and Applied Basic Research Foundation(no.2020A1515011116)+1 种基金the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(no.2016ZT06Y337)the National Science&Technology Major Project“Key New Drug Creation and Manufacturing Program”of China(no.2018ZX09711002-006).
文摘Enantioenrichedγ-butenolides are valuable structural cores in many pharmaceuticals and natural products,but their direct and catalytically asymmetric assembly remains rare.Here,we report an efficient,atom-economic synthetic strategy for enantioenrichedγ-butenolides via a unique enantioselective reaction of cyclopropene carboxylic acids with imines under the synergistic catalysis of Rh2(esp)2/chiral Brønsted acid system.The reaction involved trapping of carboxylic oxonium ylides,generated from cyclopropene carboxylic acids,which presented as the first asymmetric trapping reactive intermediate in the process.
基金This work was supported by the National Natural Science Foundation of China(Nos.81573286 and 81373259).
文摘An efficient and practical synthetic approach was developed for the tandem synthesis of trisubstituted 2-pyrone derivatives from sulfoxonium ylides and cyclopropenones.This[3+3]annulation reaction was carried out under transition-metal-free conditions.A broad range of functional groups were tolerant under mild conditions,and a variety of 2-pyrones were obtained in moderate to good yields.
基金Project supported by the National Natural Science Foundation of China
文摘The title compounds 6a—6f were prepared with high yield via intramolecular Wittig reaction of methyl 3-perfluoroalkyl-6-perfluoroacyl-2-triphenylphosphoranylidenehex-3,5-dienoates (5a—5i)which were obtained from the reaciton of 3-perfluoroacylprop-2-enylidenetriphenylphos- phoranes(3a—3c)with methyl perfluoroalkynoates(4a—4c).
文摘Asymmetric 1,3-dipolar cycloaddition of methyl a-fluoroacrylate with azomethine ylides for the construction of optically active fluorinated pyrrolidines bearing one unique fluorinated quaternary and two tertiary stereogenic cen- ters has been achieved with Cu(CH3CN)4BF4/TF-BiphamPhos complexes for the first time. This catalytic system performs well over a broad scope of substrates, providing the synthetically useful adducts in good yields and excel- lent diastereoselectivities and good to high enantioselectivities.
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Project supported by the National Natural Science Foundation of China(Nos.20225205 and 20172002),State Key Laboratory of Elemento-Organic Chemistry of Nankai University and by Trans-Century Training Programme foundation for the Talents by Ministry of Edu
文摘The first investigation on catalytic asymmetric [2,3]-sigmatrop-ic rearrangement of sulfur ylides generated from carbenoids and allenic phenyl sulfide was carried out. Up to 55% ee value was obtained.