Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,prov...Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.展开更多
Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct yn...Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.展开更多
Herein, we report a simple and efficient method for the direct installation of chlorodifluoroethyl group onto aromatic molecules of various aromatic amides with a new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt(C...Herein, we report a simple and efficient method for the direct installation of chlorodifluoroethyl group onto aromatic molecules of various aromatic amides with a new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt(CDFI). Moreover, the chlorodifluoroethyl compounds could be smoothly converted into difluorovinyl compounds in a one-pot or discrete procedure and regarded as a steady source of difluorovinyl compounds with “HCl-mask”.展开更多
A novel chiral phosphine-triazine ligand was synthesized from chiral α-phenylethylamine through a three-step procedure. In a model reaction of Pd-catalyzed allylic alkylation of rac-1,3-diphenylprop-2-en-1-y1 pivalat...A novel chiral phosphine-triazine ligand was synthesized from chiral α-phenylethylamine through a three-step procedure. In a model reaction of Pd-catalyzed allylic alkylation of rac-1,3-diphenylprop-2-en-1-y1 pivalate with dimethyl malonate, good enantioselectivity （90% e.e.） was obtained by using this ligand.展开更多
Palladium-catalyzed coupling of trifluorovinylzinc reagent with substituted aryl halides Y-C_6H_4-X (Y=p-NO_2, p-and m-COOMe, p-COOH, p-CONH_2, p- and m-CN; X=Br, I, Cl) provides a synthetic method for α, β, β-trif...Palladium-catalyzed coupling of trifluorovinylzinc reagent with substituted aryl halides Y-C_6H_4-X (Y=p-NO_2, p-and m-COOMe, p-COOH, p-CONH_2, p- and m-CN; X=Br, I, Cl) provides a synthetic method for α, β, β-trifluorostyrenes(Y-TFS's). A series of previously unavailable Y-TFS's were thus obtained.展开更多
As the chemical industry grapples with the need for more eco-friendly practices,the use of water as a reaction medium is gaining attraction in organic transformations.This mini-review delves into Pd-catalyzed reaction...As the chemical industry grapples with the need for more eco-friendly practices,the use of water as a reaction medium is gaining attraction in organic transformations.This mini-review delves into Pd-catalyzed reactions that utilize the "on-water" mechanism,spanning from 2019 to late 2023.These reactions are neatly categorized into several types: (A) Catalytic C—H activations,(B) Mizoroki- Heck-type reactions,(C) Suzuki-Miyaura reactions,and (D) Cyclization reactions.By showcasing the potential of water as a sustainable reaction medium for organic transformations,these reactions leave no doubt about the importance of embracing eco-friendly practices in the chemical industry.Key Scientists In 1980,a seminal work by Breslow et al.showed an acceleration of reaction rate in the Diels-Alder reaction.Sharpless and co-workers noted a significant increase in the rate of the [2σ+2σ+2π] cycloaddition of quadricyclane and dimethyl azodicarboxylate (DMAD) when the reaction was conducted in water,as opposed to when it was carried out in organic solvents.The term "on-water" was then coined to describe this phenomenon.This strategy was further expanded to transition-metal catalyzed transformations by Ackermann in 2011.Later,Varma and Leazer disclosed a Pd-catalyzed Mizoroki-Heck type arylation of alkenes with diaryliodonium salts “on-water”.The enantioselective version of "on-water" process was not realized until 2014 by the Zhou group.Later on,the Schaub group described a Pd-catalyzed Suzuki–Miyaura coupling reaction of electron-poor aryl chlorides with water,using only 50 ppm of catalyst loading.Very recently,Liu and Lin extended the "on-water" strategy to Pd-catalyzed double Mizoroki-Heck reactions.This mini-review has focused on Pd-catalyzed reactions involving the “on-water” mechanism.展开更多
Comprehensive Summary Pd-mediated bioorthogonal cleavage reactions have been extensively utilized in the activation of prodrug molecules,precise regulation of protein function,and cellular engineering.However,the avai...Comprehensive Summary Pd-mediated bioorthogonal cleavage reactions have been extensively utilized in the activation of prodrug molecules,precise regulation of protein function,and cellular engineering.However,the availability of cleavable"caging"groups is quite limited,and their application in nucleic acid modification has seldom been reported.Herein,we introduce a method based on Pd-catalyzed reduction amination of azides as a decaging strategy to activate the activity of biomolecules.We designed modifications on the bioactive sites with azides or their derivatives to mask the related biological function,followed by the release of biological activity through Pd-catalyzed NaBH4 reduction amination reaction.This study has demonstrated that the strategy can effectively be used to activate bioactive molecules such as fluorescent probes,prodrugs,and to regulate the biological function of RNA,including reverse transcription extension,binding to ligands,and cleavage activity of the CRISPR-Cas system.All results confirm that this strategy provides an efficient and controllable"OFF to ON"biological switch,capable of achieving significant regulatory effects substoichiometrically,and is expected to be extended to other biological applications.展开更多
Main observation and conclusion A set of Pd-catalyzed ortho-directed C-H glycosylation reactions with glycosyl chloride donors using various N-linked bidentate auxil-iaries has been developed for synthesis of C-arygly...Main observation and conclusion A set of Pd-catalyzed ortho-directed C-H glycosylation reactions with glycosyl chloride donors using various N-linked bidentate auxil-iaries has been developed for synthesis of C-aryglycosides.A broad range of pyranose and furanose moieties can be installed on the ortho position of arylamine,carbazole,indole and benzylamine type substrates in high yield and with high regio-and diastereoselec-tivity.These auxiliaries can be readily installed and removed under relatively mild conditions.展开更多
The gem-difluoromethylenated acetonide 2 was efficiently synthesized as new precursor of HMG-CoA reduc- tase inhibitor. Straightforward olefination via Pd-catalyzed C4-H activation of 1,3,5-trisubstituted pyrazoles 1 ...The gem-difluoromethylenated acetonide 2 was efficiently synthesized as new precursor of HMG-CoA reduc- tase inhibitor. Straightforward olefination via Pd-catalyzed C4-H activation of 1,3,5-trisubstituted pyrazoles 1 was proceeded smoothly in the presence of Pd（OAc）2 and AgCO3. This protocol has merits in terms of the improved atomic economy and prevention from the generation of by-products.展开更多
Pd-catalyzed carbonylation,as an efficient synthetic approach to the installation of carbonyl groups in organic compounds,has been one of the most important research fields in the past decade.Although elegant reaction...Pd-catalyzed carbonylation,as an efficient synthetic approach to the installation of carbonyl groups in organic compounds,has been one of the most important research fields in the past decade.Although elegant reactions that allow highly selective carbonylations have been developed,straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications.Here,we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources.A broad range of aryl iodides and alcohols are compatible with this protocol.The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction.In addition,the reaction affords lactones and lactams in an intermolecular fashion.Moreover,DFT calculations have been performed to study the detailed mechanisms.展开更多
An efficient synthesis of substituted 1,4-diazepines is developed.The accessible intermediates have been obtained via Pd-catalyzed amination.The subsequent hydrogenation and intramolecular condensation sequences could...An efficient synthesis of substituted 1,4-diazepines is developed.The accessible intermediates have been obtained via Pd-catalyzed amination.The subsequent hydrogenation and intramolecular condensation sequences could be conducted successively in one pot without special operation.The mild and general strategy enables the synthesis of various substituted 1,4-diazepines in high yields.展开更多
Efficient synthetic routs for the direct and rapid construction of[5-6-6]ABC tricyclic systems of daphmanidin A-type and calyciphylline A-type alkaloids have been successfully developed.For the daphmanidin A-type,the ...Efficient synthetic routs for the direct and rapid construction of[5-6-6]ABC tricyclic systems of daphmanidin A-type and calyciphylline A-type alkaloids have been successfully developed.For the daphmanidin A-type,the synthesis of[5-6-6]tricyclic framework utilize a HCl-mediated intramolecular Aldol reaction to construct the bicyclo[2.2.2]octane core and a thermal condensation to afford the ABC ring system.In addition,for the calyciphylline A-type,an improved synthesis of ABC[5-6-6]tricyclic system was developed,featuring an introduction of methyl ester group at C2 before the Pd-catalyzed intramolecular oxidative alkylation to construct the desired bowl-shape tricyclic core with stereochemical control.展开更多
A novel chiral bis(ferrocenyl) P2N ligand 1 with C2-symmetry was synthesized through a four-step procedure from (R)-N,N-dimethyl-1-ferrocenylethylamine. In a model reaction of Pd-catalyzed allylic alkylation of 1,3-d...A novel chiral bis(ferrocenyl) P2N ligand 1 with C2-symmetry was synthesized through a four-step procedure from (R)-N,N-dimethyl-1-ferrocenylethylamine. In a model reaction of Pd-catalyzed allylic alkylation of 1,3-diphenylprop-2-enyl acetate 6 with dimethyl malonate, good enantioselectivity (86% e.e.) was obtained.展开更多
A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This ...A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.展开更多
We developed a novel Pd-catalyzed carbonylation of ortho-alkenyl iodobenzenes with co,affording a diverse array of 3-arylindenones in good to excellent yields(up to 94%yield).This methodology exhibits broad substrate ...We developed a novel Pd-catalyzed carbonylation of ortho-alkenyl iodobenzenes with co,affording a diverse array of 3-arylindenones in good to excellent yields(up to 94%yield).This methodology exhibits broad substrate scope and good functional group compatibility.The synthetic utility was demonstrated by a gram-scale reaction,diverse product derivatizations,and the preparation of an intermediateforaPPARyagonist.展开更多
Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylatio...Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.展开更多
We report a palladium-catalyzed asymmetric[4+4]cycloaddition reaction between 2-alkylidenetrimethylene carbonate and electron-deficient indole-2,3-quinodimethanes(IQDMs).This reaction features exclusive regioselectivi...We report a palladium-catalyzed asymmetric[4+4]cycloaddition reaction between 2-alkylidenetrimethylene carbonate and electron-deficient indole-2,3-quinodimethanes(IQDMs).This reaction features exclusive regioselectivity,high yield(up to 98%),excellent enantioselectivity(up to 95%ee),and easy scale-up without any loss of efficiency,making it valuable for the synthesis of indole-fused eight-membered oxa-rings.展开更多
The Pd-catalyzed addition of carbon monoxide and carbon tetrachloride to 1-octene gave coadduct [alkyl 2-(2,2,2-trichloroethyl)octanoate] as the major product in supercritical carbon dioxide by using pyridine as the b...The Pd-catalyzed addition of carbon monoxide and carbon tetrachloride to 1-octene gave coadduct [alkyl 2-(2,2,2-trichloroethyl)octanoate] as the major product in supercritical carbon dioxide by using pyridine as the base. It was found that the selectivity and the yield of coadduct were greatly affected by the pressure of carbon dioxide,the reaction temperature and the amounts of alcohol and base used.展开更多
We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azoci...We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.展开更多
基金financial support from the National Natural Science Foundation of China(Nos.22271024,21632005)Changzhou University.
文摘Double bonds of internal olefins can be efficiently migrated to the terminal carbons and regioselectively hydroesterified with formates in the presence of Pd(OAc)_(2) and 1,2-DTBPMB under mild reaction conditions,providing a wide variety of corresponding linear carboxylic esters bearing various functional groups in good yields and>20:1 linear/branch ratios.The reaction is optionally simple and does not need to use CO gas and acid co-catalysts.
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
基金supported by the National Key Research and Development Program of China (No. 2016YFB0401400)the National Natural Science Foundation of China (Nos. 22071129, 21871158 and21672120)。
文摘Herein, we report a simple and efficient method for the direct installation of chlorodifluoroethyl group onto aromatic molecules of various aromatic amides with a new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt(CDFI). Moreover, the chlorodifluoroethyl compounds could be smoothly converted into difluorovinyl compounds in a one-pot or discrete procedure and regarded as a steady source of difluorovinyl compounds with “HCl-mask”.
文摘A novel chiral phosphine-triazine ligand was synthesized from chiral α-phenylethylamine through a three-step procedure. In a model reaction of Pd-catalyzed allylic alkylation of rac-1,3-diphenylprop-2-en-1-y1 pivalate with dimethyl malonate, good enantioselectivity （90% e.e.） was obtained by using this ligand.
基金Supported by National Natural Science Foundation of China
文摘Palladium-catalyzed coupling of trifluorovinylzinc reagent with substituted aryl halides Y-C_6H_4-X (Y=p-NO_2, p-and m-COOMe, p-COOH, p-CONH_2, p- and m-CN; X=Br, I, Cl) provides a synthetic method for α, β, β-trifluorostyrenes(Y-TFS's). A series of previously unavailable Y-TFS's were thus obtained.
基金support from the National Natural Science Foundation of China(22101296)the State Key Laboratory of Systems Medicine for Cancer(SB23-09,KF2130-93).
文摘As the chemical industry grapples with the need for more eco-friendly practices,the use of water as a reaction medium is gaining attraction in organic transformations.This mini-review delves into Pd-catalyzed reactions that utilize the "on-water" mechanism,spanning from 2019 to late 2023.These reactions are neatly categorized into several types: (A) Catalytic C—H activations,(B) Mizoroki- Heck-type reactions,(C) Suzuki-Miyaura reactions,and (D) Cyclization reactions.By showcasing the potential of water as a sustainable reaction medium for organic transformations,these reactions leave no doubt about the importance of embracing eco-friendly practices in the chemical industry.Key Scientists In 1980,a seminal work by Breslow et al.showed an acceleration of reaction rate in the Diels-Alder reaction.Sharpless and co-workers noted a significant increase in the rate of the [2σ+2σ+2π] cycloaddition of quadricyclane and dimethyl azodicarboxylate (DMAD) when the reaction was conducted in water,as opposed to when it was carried out in organic solvents.The term "on-water" was then coined to describe this phenomenon.This strategy was further expanded to transition-metal catalyzed transformations by Ackermann in 2011.Later,Varma and Leazer disclosed a Pd-catalyzed Mizoroki-Heck type arylation of alkenes with diaryliodonium salts “on-water”.The enantioselective version of "on-water" process was not realized until 2014 by the Zhou group.Later on,the Schaub group described a Pd-catalyzed Suzuki–Miyaura coupling reaction of electron-poor aryl chlorides with water,using only 50 ppm of catalyst loading.Very recently,Liu and Lin extended the "on-water" strategy to Pd-catalyzed double Mizoroki-Heck reactions.This mini-review has focused on Pd-catalyzed reactions involving the “on-water” mechanism.
基金the National Natural Science Foundation of China(Nos.22177089,21721005,92153303,22037004,22177088)the Fundamental Research Funds for the Central Universities(2042021kf0211)Translational Medicine and Interdisciplinary Research Joint Fund of Zhongnan Hospital of Wuhan University(Grant No.ZNJC202309).
文摘Comprehensive Summary Pd-mediated bioorthogonal cleavage reactions have been extensively utilized in the activation of prodrug molecules,precise regulation of protein function,and cellular engineering.However,the availability of cleavable"caging"groups is quite limited,and their application in nucleic acid modification has seldom been reported.Herein,we introduce a method based on Pd-catalyzed reduction amination of azides as a decaging strategy to activate the activity of biomolecules.We designed modifications on the bioactive sites with azides or their derivatives to mask the related biological function,followed by the release of biological activity through Pd-catalyzed NaBH4 reduction amination reaction.This study has demonstrated that the strategy can effectively be used to activate bioactive molecules such as fluorescent probes,prodrugs,and to regulate the biological function of RNA,including reverse transcription extension,binding to ligands,and cleavage activity of the CRISPR-Cas system.All results confirm that this strategy provides an efficient and controllable"OFF to ON"biological switch,capable of achieving significant regulatory effects substoichiometrically,and is expected to be extended to other biological applications.
基金G.C.thanks NSFC-91753124,NSFC-21672105,NSFC-21421062,and NSFC-21725204 for financial support of this work.
文摘Main observation and conclusion A set of Pd-catalyzed ortho-directed C-H glycosylation reactions with glycosyl chloride donors using various N-linked bidentate auxil-iaries has been developed for synthesis of C-aryglycosides.A broad range of pyranose and furanose moieties can be installed on the ortho position of arylamine,carbazole,indole and benzylamine type substrates in high yield and with high regio-and diastereoselec-tivity.These auxiliaries can be readily installed and removed under relatively mild conditions.
基金supported by the National Natural Science Foundation of China （Nos. 20972050, 21172148 and 21202044） and the Science and Technology Commission of Shanghai Municipality （No. 10540501300）.
文摘The gem-difluoromethylenated acetonide 2 was efficiently synthesized as new precursor of HMG-CoA reduc- tase inhibitor. Straightforward olefination via Pd-catalyzed C4-H activation of 1,3,5-trisubstituted pyrazoles 1 was proceeded smoothly in the presence of Pd（OAc）2 and AgCO3. This protocol has merits in terms of the improved atomic economy and prevention from the generation of by-products.
基金supported by the Science Foundation for Distinguished Young Scholars for Guangdong Province(2020B1515020026)the Science and Technology Program of Guangzhou(202103000089)+6 种基金the Innovation Team Project of Universities in Guangdong Province(2020KCXTD009)the Scientific Research Projects for Key Disciplines of Guangdong Province(2019-GDXK-0009)the Key Projects of Social Welfare and Basic Research of Zhongshan City(2020B2007)the Innovation and Strong School Project of Guangdong Pharmaceutical University(2018KQNCX131)Guangdong Cosmetics Engineering&Technology Research CenterProvincial Experimental Teaching Demonstration Center of Chemistry&Chemical EngineeringSpecial Funds of Key Disciplines Construction from Guangdong and Zhongshan Cooperating。
文摘Pd-catalyzed carbonylation,as an efficient synthetic approach to the installation of carbonyl groups in organic compounds,has been one of the most important research fields in the past decade.Although elegant reactions that allow highly selective carbonylations have been developed,straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications.Here,we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources.A broad range of aryl iodides and alcohols are compatible with this protocol.The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction.In addition,the reaction affords lactones and lactams in an intermolecular fashion.Moreover,DFT calculations have been performed to study the detailed mechanisms.
基金supported by National Natural Science Foundation of China(No.81102322)
文摘An efficient synthesis of substituted 1,4-diazepines is developed.The accessible intermediates have been obtained via Pd-catalyzed amination.The subsequent hydrogenation and intramolecular condensation sequences could be conducted successively in one pot without special operation.The mild and general strategy enables the synthesis of various substituted 1,4-diazepines in high yields.
基金supported by the National Natural Science Foundation of China(No.21502011)the Fundamental Research Funds for the Central Universitiesthe Chongqing Science&Technology Commission Project(No.cstc2016jcyjA0168)。
文摘Efficient synthetic routs for the direct and rapid construction of[5-6-6]ABC tricyclic systems of daphmanidin A-type and calyciphylline A-type alkaloids have been successfully developed.For the daphmanidin A-type,the synthesis of[5-6-6]tricyclic framework utilize a HCl-mediated intramolecular Aldol reaction to construct the bicyclo[2.2.2]octane core and a thermal condensation to afford the ABC ring system.In addition,for the calyciphylline A-type,an improved synthesis of ABC[5-6-6]tricyclic system was developed,featuring an introduction of methyl ester group at C2 before the Pd-catalyzed intramolecular oxidative alkylation to construct the desired bowl-shape tricyclic core with stereochemical control.
基金supported by the National Natural Science Foundation of China(29933050)
文摘A novel chiral bis(ferrocenyl) P2N ligand 1 with C2-symmetry was synthesized through a four-step procedure from (R)-N,N-dimethyl-1-ferrocenylethylamine. In a model reaction of Pd-catalyzed allylic alkylation of 1,3-diphenylprop-2-enyl acetate 6 with dimethyl malonate, good enantioselectivity (86% e.e.) was obtained.
基金financially supported by the National Natural Science Foundation of China(No.21202116)Independent Innovation Foundation of Tianjin Universityof China(No.2016XZC-0071)Natural Science Foundation of Tianjin of China(No.16JCYBJC20300)
文摘A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.
基金support from the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01007)the NSFC(22301280),and the Start-up Research Grant from Zhejiang Normal University.
文摘We developed a novel Pd-catalyzed carbonylation of ortho-alkenyl iodobenzenes with co,affording a diverse array of 3-arylindenones in good to excellent yields(up to 94%yield).This methodology exhibits broad substrate scope and good functional group compatibility.The synthetic utility was demonstrated by a gram-scale reaction,diverse product derivatizations,and the preparation of an intermediateforaPPARyagonist.
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.
基金support from the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01007)the NSFC(22171082,22201253)+1 种基金the Start-up Research Grant from Zhejiang Normal Universitythe Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism.
文摘We report a palladium-catalyzed asymmetric[4+4]cycloaddition reaction between 2-alkylidenetrimethylene carbonate and electron-deficient indole-2,3-quinodimethanes(IQDMs).This reaction features exclusive regioselectivity,high yield(up to 98%),excellent enantioselectivity(up to 95%ee),and easy scale-up without any loss of efficiency,making it valuable for the synthesis of indole-fused eight-membered oxa-rings.
文摘The Pd-catalyzed addition of carbon monoxide and carbon tetrachloride to 1-octene gave coadduct [alkyl 2-(2,2,2-trichloroethyl)octanoate] as the major product in supercritical carbon dioxide by using pyridine as the base. It was found that the selectivity and the yield of coadduct were greatly affected by the pressure of carbon dioxide,the reaction temperature and the amounts of alcohol and base used.
基金We are grateful for financial support from National Key Research and Development Program of China(2021YFA0804900)the NSFC(22171082,21971062)+1 种基金the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2022R01007)Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism.
文摘We developed a novel Pd-catalyzed[4+4]cycloaddition of(benzo)furan-derived azadienes with homo-TMM all-carbon 1,4-dipoles in situ generated fromα-allyl malonate derivatives,affording an array of benzofuro[3,2-b]azocines and furo[3,2-b]azocines with good to excellent yields(up to 96%)and exclusive regioselectivities.This methodology featured mild reaction conditions and good functional group tolerance.The synthetic utility was demonstrated by a gram-scale reaction.Furthermore,the catalytic asymmetric[4+4]cycloaddition version has also been explored.
