A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cy...A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cyclic protected amines were readily synthesized without requiring exogenous transition-metal or photoredox catalysts.Moreover,this ap-proach facilitates late-stage functionalization of complex molecules and is amenable to continuous-flow process on gram scale.展开更多
Herein,we describe a nickel-catalyzed reductive decarboxylative difluoromethylation reaction of alkenes using inexpensive and easy-to-handle difluoroacetic anhydride(DFAA)/pyridine N-oxide reagent system.A variety of ...Herein,we describe a nickel-catalyzed reductive decarboxylative difluoromethylation reaction of alkenes using inexpensive and easy-to-handle difluoroacetic anhydride(DFAA)/pyridine N-oxide reagent system.A variety of C(sp^(3))-CF_(2)H containing compounds were prepared through a hydrodifluoromethylation process.Besides,various gem–difluoroalkenes bearing CF_(2)H group were synthesized via defluorinative reductive cross-coupling process from trifluoromethyl-substituted alkenes using this new reaction system.Difluoroacetic anhydride has been then extended to other common alkyl anhydrides,and the corresponding hydroalkylation and defluoroalkylation processes have been successfully achieved.This method features broad substrate scope,good functional group tolerance as well as high efficiency.展开更多
Alduronic acid lactones and glyconolactones are highly functionalized and versatile chiral building blocks.Herein,we describe a novel approach to these compounds via decarboxylative oxygenation of uronic acids.The tra...Alduronic acid lactones and glyconolactones are highly functionalized and versatile chiral building blocks.Herein,we describe a novel approach to these compounds via decarboxylative oxygenation of uronic acids.The transformations proceed using Selectfluor and TEMPO as oxidants,either in the presence of catalytic amounts of Ag_(2)CO_(3)or in the absence of this catalyst.The methodology provides structurally diverse alduronic acid lactones and enables the preparation of rare sugar glyconolactones from easily available D-C-glycosides.Based on the^(18)O-labeling experiments,control experiments,and isolation of the key intermediates,a radical-polar crossover reaction mechanism is proposed.The utility of this method is demonstrated through efficient conversions of alduronic acid lactones into polyhydroxylated cyclic alkaloids and castanospermine-type architectures.展开更多
A convenient and general method for acylation of free （N-H） indoles via palladium-catalyzed decarboxylative cross-coupling reaction was developed. This process provided a useful method for the preparation of diverse...A convenient and general method for acylation of free （N-H） indoles via palladium-catalyzed decarboxylative cross-coupling reaction was developed. This process provided a useful method for the preparation of diverse 3-acylindoles in high yields utilizing a reaction with readily accessible reactants under mild conditions,展开更多
Highly active and stable magnetic copper catalysts were successfully achieved by magnetic induced Stober method and subsequent hydrothermal reaction with copper ions in alkaline condition.The high content of Cu2+as we...Highly active and stable magnetic copper catalysts were successfully achieved by magnetic induced Stober method and subsequent hydrothermal reaction with copper ions in alkaline condition.The high content of Cu2+as well as the unique structures of hierarchical copper silicate in the as-prepared catalysts endowed their outstanding catalytic performance.Efficient decarboxylative A3-coupling of a-keto acid,amine and alkyne was realized with the low Fe3 O4@CuSiO3 loading.A range of propargylamines were produced in good to excellent yields under solvent-free condition.Moreover,the catalyst can be easily separated from the final organic product with an external magnet.Also,this kind of catalyst could be recycled up to six times while maintaining its activity.展开更多
A novel bromination of α,β-unsaturated carboxylic acids was developed via a decarboxylation by virtue of a direct anodic electro-oxidation.In this method,ammonium bromide was employed as a bromine source and the rea...A novel bromination of α,β-unsaturated carboxylic acids was developed via a decarboxylation by virtue of a direct anodic electro-oxidation.In this method,ammonium bromide was employed as a bromine source and the reaction features transition-metal-free,short time,and no additional supporting electrolyte.展开更多
A novel nitro-coordinated potassium compound [K(Htdc)(H_2O)]_n(tdc = 3-nitro-thiophene-2,5-dicarboxylate), has been synthesized and characterized. The complex with a two-dimensional(2D) layer structure contains an inf...A novel nitro-coordinated potassium compound [K(Htdc)(H_2O)]_n(tdc = 3-nitro-thiophene-2,5-dicarboxylate), has been synthesized and characterized. The complex with a two-dimensional(2D) layer structure contains an infinite K-O ladder-shaped chain, which is connected through carboxyl and unusual nitro-coordination of Htdc– anion. Then the 2D layers are further extended by intermolecular hydrogen-bonding to form a three-dimensional(3D) supramoleculalr network. Variable temperature powder X-ray diffractions, thermogravimetric analysis and nuclear magnetic resonance studies exhibit that the compound has a thermal-induced decarboxylative behavior.展开更多
A novel and general carbon-nitrogen and carbon-carbon cross-coupling reaction between 3,4-dihydropyrimidine-2-thiones and copper（Ⅰ） carboxylates were performed in the presence of palladium acetate.The copper（Ⅰ） ...A novel and general carbon-nitrogen and carbon-carbon cross-coupling reaction between 3,4-dihydropyrimidine-2-thiones and copper（Ⅰ） carboxylates were performed in the presence of palladium acetate.The copper（Ⅰ） carboxylates act not only as desulfurative reagents but also as sources of carbon nudeophiles.A wide array of highly substituted and functionalized pyrimidines scaffolds were synthesized in good yields.展开更多
Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good ...Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.展开更多
An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources ...An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources such as methanol are not needed in this catalytic system. This reaction could be performed successfully under ligand- and base-free conditions. It demonstrated that phenylpropiolic acids can be employed as alkyne synthons in the hydroboration reaction and exhibited good reactivity and higher selectivity than terminal alkynes.展开更多
A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of pr...A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.展开更多
An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of th...An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of the reaction is the compatibility of diboron reagents with the electrochemical conditions. This reaction exhibits broad substrate scope, good functional group tolerability, and easy scalability.展开更多
Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of thi...Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.展开更多
An efficient method for Cu-catalyzed decarboxylative trifluoromethylation offl-ketoacids to achieve a-trifluoro- methyl ketones was developed. A wide variety of synthetically useful α-trifluoromethyl ketones were obt...An efficient method for Cu-catalyzed decarboxylative trifluoromethylation offl-ketoacids to achieve a-trifluoro- methyl ketones was developed. A wide variety of synthetically useful α-trifluoromethyl ketones were obtained in modest to good yields under mild reaction conditions. The present method also exhibits good functional-group compatibility.展开更多
The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocataly...The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocatalytic decarboxylative alkynylation approach.By utilizing an iridium photocatalyst in the presence of visible light,glycosyl radicals are in-situ generated via the decarboxylation of anomeric acids and efficiently coupled with a variety of ethynylbenziodoxolones(EBXs),which allows the facile synthesis of a variety of alkynyl C-glycosides in moderate to high yields and with excellent diastereoselectivity.展开更多
Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential i...Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential in running decarboxylation to construct ketone derivatives.In this article,we have developed a photocatalytic decarboxylative cross-coupling ofα-oxocarboxylic acids and olefins to the synthesis of diverse aryl ketones.Various alkenes andα-oxocarboxylicacids were compatible,generating the desired products in up to 90%yield.Preliminary mechanism studies suggest that a free radical pathway is involved in this process.展开更多
Nitrogen-containing motifs are widely present in natural products, bioactive molecules, and drugs. Accordingly, effective synthetic methods with high efficiency and diversity are highly desirable. Here, we present the...Nitrogen-containing motifs are widely present in natural products, bioactive molecules, and drugs. Accordingly, effective synthetic methods with high efficiency and diversity are highly desirable. Here, we present the invention of a facile, visible lightmediated decarboxylative C(sp^(3))–N bond-forming reaction by employing abundant carboxylic acids as the feedstock and a commercial diazirine as a nitrogen donor. This process is amenable to access both imines and diaziridines, as the corresponding masked amines and hydrazines, through a selectable single or double nitrogen transfer from the diazirine, respectively. This divergent approach works well in both directions with various alkyl carboxylic acids, including primary, secondary, and tertiary acids, as well as natural products and drugs, thus affording a rapid, metal-free approach to build nitrogen-containing molecule libraries with considerable structural diversity, which could thus benefit the related study in context of chemical biology and drug discovery.展开更多
A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition t...A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition to unsaturated bond followed by intramolecular addition to arene, with a broad scope of N-hydroxyphthalimide derived redox active esters under visible light irradiation. The reactions are suggested to proceed through photoactivation of a transiently assembled chromophore from electron-deficient phthalimide moiety and iodide anion through an anion-π interaction in solvent cage followed by diffusion to generate solvated free radical species to react with C-H substrates. The simplicity, practicality, and broad substrate scope of this method highlight the synthetic power of photocatalysis through transiently assembled chromophore, and will hopefully inspire further developments of low cost photocatalysis based on various non-covalent interactions, which are prevalent in supramolecular chemistry and biosystems, for sustainable organic synthesis.展开更多
A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic e...A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic ethers. Mechanism study shows the reaction involves a radical process.展开更多
Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed deca...Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters.A wide range of structurally diverse asymmetrical aryl alkyl and dialkyl ketones have been constructed in yields of up to 98% with this strategy.The protocol has excellent reaction selectivity and functional group compatibility,representing a significant step forward in ketone synthesis.The one-pot decarboxylative acylation at the gram scale from two different carboxylic acids and the late-stage application for the synthesis of complex ketones shows its synthetic robustness.Both mechanistic experiments and density functional theory(DFT)calculations suggest that the decarboxylative acylation reaction operates via an underdeveloped Ni(Ⅰ)-Ni(Ⅱ)-Ni(Ⅰ)-Ni(Ⅲ)-Ni(Ⅰ)catalytic cycle.展开更多
文摘A facile method for decarboxylative amination driven by the photoactivity of electron donor-acceptor(EDA)com-plexes assembled from iodide salts and redox-active esters has been proposed.A broad array of acyclic and cyclic protected amines were readily synthesized without requiring exogenous transition-metal or photoredox catalysts.Moreover,this ap-proach facilitates late-stage functionalization of complex molecules and is amenable to continuous-flow process on gram scale.
基金financial support from the National Natural Science Foundation of China(NSFC,No.21877067)Tsinghua-Peking Centre for Life Science。
文摘Herein,we describe a nickel-catalyzed reductive decarboxylative difluoromethylation reaction of alkenes using inexpensive and easy-to-handle difluoroacetic anhydride(DFAA)/pyridine N-oxide reagent system.A variety of C(sp^(3))-CF_(2)H containing compounds were prepared through a hydrodifluoromethylation process.Besides,various gem–difluoroalkenes bearing CF_(2)H group were synthesized via defluorinative reductive cross-coupling process from trifluoromethyl-substituted alkenes using this new reaction system.Difluoroacetic anhydride has been then extended to other common alkyl anhydrides,and the corresponding hydroalkylation and defluoroalkylation processes have been successfully achieved.This method features broad substrate scope,good functional group tolerance as well as high efficiency.
基金financial support from the Marine S&T Fund of Shandong Province for Qingdao Marine Science and Technology Center(No.2022QNLM030003-2)the National Key Research&Development Program of China(No.2022YFA2104902)the National Natural Science Foundation of China(Nos.21977088 and22377114)。
文摘Alduronic acid lactones and glyconolactones are highly functionalized and versatile chiral building blocks.Herein,we describe a novel approach to these compounds via decarboxylative oxygenation of uronic acids.The transformations proceed using Selectfluor and TEMPO as oxidants,either in the presence of catalytic amounts of Ag_(2)CO_(3)or in the absence of this catalyst.The methodology provides structurally diverse alduronic acid lactones and enables the preparation of rare sugar glyconolactones from easily available D-C-glycosides.Based on the^(18)O-labeling experiments,control experiments,and isolation of the key intermediates,a radical-polar crossover reaction mechanism is proposed.The utility of this method is demonstrated through efficient conversions of alduronic acid lactones into polyhydroxylated cyclic alkaloids and castanospermine-type architectures.
基金the financial support from the State Ethnic Affairs Commission(No.12YNZ005)
文摘A convenient and general method for acylation of free （N-H） indoles via palladium-catalyzed decarboxylative cross-coupling reaction was developed. This process provided a useful method for the preparation of diverse 3-acylindoles in high yields utilizing a reaction with readily accessible reactants under mild conditions,
基金supported by the National Natural Science Foundation of China(Nos.21601121,21305086)the Natural Science Foundation of Shanghai(No.18ZR1416400)+1 种基金support of the Shanghai University of Engineering Science(Nos.201810856017,A1-0601-19-01017)the Opening Project of Shanghai Key Laboratory of Chemical Biology for financial support。
文摘Highly active and stable magnetic copper catalysts were successfully achieved by magnetic induced Stober method and subsequent hydrothermal reaction with copper ions in alkaline condition.The high content of Cu2+as well as the unique structures of hierarchical copper silicate in the as-prepared catalysts endowed their outstanding catalytic performance.Efficient decarboxylative A3-coupling of a-keto acid,amine and alkyne was realized with the low Fe3 O4@CuSiO3 loading.A range of propargylamines were produced in good to excellent yields under solvent-free condition.Moreover,the catalyst can be easily separated from the final organic product with an external magnet.Also,this kind of catalyst could be recycled up to six times while maintaining its activity.
基金the National Nature Science Foundation of China(Nos.21472177,21672200,21432009,J1310010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)
文摘A novel bromination of α,β-unsaturated carboxylic acids was developed via a decarboxylation by virtue of a direct anodic electro-oxidation.In this method,ammonium bromide was employed as a bromine source and the reaction features transition-metal-free,short time,and no additional supporting electrolyte.
基金supported by the Natural Science Foundation of Henan Province(172102210410 and 172102310476)
文摘A novel nitro-coordinated potassium compound [K(Htdc)(H_2O)]_n(tdc = 3-nitro-thiophene-2,5-dicarboxylate), has been synthesized and characterized. The complex with a two-dimensional(2D) layer structure contains an infinite K-O ladder-shaped chain, which is connected through carboxyl and unusual nitro-coordination of Htdc– anion. Then the 2D layers are further extended by intermolecular hydrogen-bonding to form a three-dimensional(3D) supramoleculalr network. Variable temperature powder X-ray diffractions, thermogravimetric analysis and nuclear magnetic resonance studies exhibit that the compound has a thermal-induced decarboxylative behavior.
基金Financial support from the National Natural Science Foundation of China(Nos.21362032 and 21362031)the NSF of Gansu Province(No.1208RJYA083)
文摘A novel and general carbon-nitrogen and carbon-carbon cross-coupling reaction between 3,4-dihydropyrimidine-2-thiones and copper（Ⅰ） carboxylates were performed in the presence of palladium acetate.The copper（Ⅰ） carboxylates act not only as desulfurative reagents but also as sources of carbon nudeophiles.A wide array of highly substituted and functionalized pyrimidines scaffolds were synthesized in good yields.
基金financially supported by the National Natural Science Foundation of China(Nos.21402116,21502111,21572126)the Science and Technology Innovation Talents of Henan Province(No.2018JQ0011)the Key Science Research of Education Committee in Henan Province(No.21A150044)。
文摘Silver-catalyzed decarboxylative C–H alkylation of cyclic aldimines with abundant aliphatic carboxylic acids has been realized under mild reaction conditions generating the corresponding products in moderate to good yields(32%–91%).In addition,a gram-scale reaction,late-stage modification of drug,synthetic transformation of the product,and further application of the catalytic strategy were also performed.Preliminary studies indicate that the reaction undergoes a radical process.
基金Financial support from the National Science Foundation of China (No. 21202049)the Recruitment Program of Global Experts (1000 Talents Plan)+2 种基金Fujian Hundred Talents PlanProgram of Innovative Research Team of Huaqiao UniversityInstrumental Analysis Center of Huaqiao University for analysis support
文摘An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources such as methanol are not needed in this catalytic system. This reaction could be performed successfully under ligand- and base-free conditions. It demonstrated that phenylpropiolic acids can be employed as alkyne synthons in the hydroboration reaction and exhibited good reactivity and higher selectivity than terminal alkynes.
基金Financial support from the National Natural Science Foundation of China(Nos.81803484,21602158)Zhejiang Provincial Natural Science Foundation(No.LY19B020011)Public Welfare Science and Technology Project of Wenzhou(Nos.Y20190132,Y20180233)are greatly appreciated.
文摘A novel and efficient copper-catalyzed decarboxylative alkynylselenation of indoles with Se powder and propiolic acids has been developed.The outstanding advantages of this protocol not only nicely avoid the use of prefabricated arylselenation reagent and address the facile over-selention issues,but also enrich the chemistry of selenium powder.Importantly,this reaction could be extended to pyrrole,and the practical utility of this transformation has been demonstrated in gram-scale synthesis and late-stage indolylselenation of Clofibrate-derived propiolic acid.
基金supported by the National Natural Science Foundation of China (Nos. 21871074 and 21971051)the National Key R&D Program of China (No. 2018YFB1501604)+1 种基金the Fundamental Research Funds for the Central Universities (No. PA2020GDKC0021)the Key Research and Development Program Projects in Anhui Province (No. 201904a07020069)。
文摘An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal-or photo-catalysts. The key feature of the reaction is the compatibility of diboron reagents with the electrochemical conditions. This reaction exhibits broad substrate scope, good functional group tolerability, and easy scalability.
基金supported by the National Natural Science Foundation of China(No.21702119)Natural Science Foundation of Shandong Province(Nos.ZR2016JL012,ZR2020JQ07)the Scientific Research Foundation of Qingdao University of Science and Technology(No.1203043003457)。
文摘Transition-metal-catalyzed decarboxylative and C–H functionalization strategy for the construction of Csp^(2)-Csp^(2),Csp^(2)-Csp,and Csp^(2)-Csp^(3) bonds has been extensively studied.However,research surveys of this synthetic strategy for the Csp^(3)-Csp^(3) bond forming reactions are surprisingly scarce.Herein,we present an efficient approach for the rapid formation of Csp^(3)–Csp^(3) bond through copper-catalyzed decarboxylative Csp^(3)–H functionalization.The present method should provide a useful access to C3-substituted indole scaffolds with possible biological activities.Mechanistic experiments and DFT calculations supported a dual-Cu(Ⅱ)-catalytic cycle involving rate-determining decarboxylation in an outer-sphere radical pathway and spin-crossover-promoted C–C bond formation.This strategy offers a promising synthesis method for the construction of Csp^(3)–Csp^(3) bond in the field of synthetic and pharmaceutical chemistry and extends the number of still limited copper-catalyzed decarboxylative Csp^(3)–Csp^(3) bond forming reaction.
基金We gratefully acknowledge financial support from the National Natural Science Foundation of China （21472033） and the Fundamental Research Funds for the Central Universities. We thank Wen-Man Zhang and Bei Huang in this group for reproducing the results of compounds 3c, 3e, and 3m.
文摘An efficient method for Cu-catalyzed decarboxylative trifluoromethylation offl-ketoacids to achieve a-trifluoro- methyl ketones was developed. A wide variety of synthetically useful α-trifluoromethyl ketones were obtained in modest to good yields under mild reaction conditions. The present method also exhibits good functional-group compatibility.
基金Financial support from the program of the National Natural Science Foundation of China(No.21871086,Y.-Q.Z.)is gratefully acknowledged.
文摘The highly stereoselective synthesis of diverse medicinally valuable alkynyl C-glycosides under mild and green reaction conditions remains a great challenge.Herein,we wish to report a visible-light induced photocatalytic decarboxylative alkynylation approach.By utilizing an iridium photocatalyst in the presence of visible light,glycosyl radicals are in-situ generated via the decarboxylation of anomeric acids and efficiently coupled with a variety of ethynylbenziodoxolones(EBXs),which allows the facile synthesis of a variety of alkynyl C-glycosides in moderate to high yields and with excellent diastereoselectivity.
基金supported by the National Natural Science Foundation of China(21520102003,21702081,21702152)the Hubei Province Natural Science Foundation of China(2017CFA010)the Program of Introducing Talents of Discipline to Universities of China(111 Program)
文摘Photocatalytic decarboxylative cross-coupling which achieves the derivatization of widespread organic acids has become a hot topic in organic synthesis.As special acids,α-oxocarboxylicacids show the great potential in running decarboxylation to construct ketone derivatives.In this article,we have developed a photocatalytic decarboxylative cross-coupling ofα-oxocarboxylic acids and olefins to the synthesis of diverse aryl ketones.Various alkenes andα-oxocarboxylicacids were compatible,generating the desired products in up to 90%yield.Preliminary mechanism studies suggest that a free radical pathway is involved in this process.
基金the National Natural Science Foundation of China(21602028)Beijing National Laboratory for Molecular Sciences(BNLMS201913)+1 种基金the Recruitment Program of Global ExpertsFuzhou University。
文摘Nitrogen-containing motifs are widely present in natural products, bioactive molecules, and drugs. Accordingly, effective synthetic methods with high efficiency and diversity are highly desirable. Here, we present the invention of a facile, visible lightmediated decarboxylative C(sp^(3))–N bond-forming reaction by employing abundant carboxylic acids as the feedstock and a commercial diazirine as a nitrogen donor. This process is amenable to access both imines and diaziridines, as the corresponding masked amines and hydrazines, through a selectable single or double nitrogen transfer from the diazirine, respectively. This divergent approach works well in both directions with various alkyl carboxylic acids, including primary, secondary, and tertiary acids, as well as natural products and drugs, thus affording a rapid, metal-free approach to build nitrogen-containing molecule libraries with considerable structural diversity, which could thus benefit the related study in context of chemical biology and drug discovery.
基金supported by the National Natural Science Foundation of China(GG2065010002)and KY(2060000119)support from the Fundamental Research Funds for the Central Universities(WK2060120003)Anhui Provincial Natural Science Foundation(1908085QB53)。
文摘A simple ammonium iodide salt in amide solvent catalyzes regioselective decarboxylative alkylation of C(sp^(3))-H bonds of Naryl glycine derivatives, of C(sp^(2))-H bond of heteroarenes, and cascade radical addition to unsaturated bond followed by intramolecular addition to arene, with a broad scope of N-hydroxyphthalimide derived redox active esters under visible light irradiation. The reactions are suggested to proceed through photoactivation of a transiently assembled chromophore from electron-deficient phthalimide moiety and iodide anion through an anion-π interaction in solvent cage followed by diffusion to generate solvated free radical species to react with C-H substrates. The simplicity, practicality, and broad substrate scope of this method highlight the synthetic power of photocatalysis through transiently assembled chromophore, and will hopefully inspire further developments of low cost photocatalysis based on various non-covalent interactions, which are prevalent in supramolecular chemistry and biosystems, for sustainable organic synthesis.
基金supported by the National Natural Science Foundation of China (21572240)
文摘A copper-catalyzed decarboxylative oxidative coupling of α,β-unsaturated carboxylic acids with non-cyclic ethers is developed.This method provides a new approach for C(sp^3)–H bond functionalization of non-cyclic ethers. Mechanism study shows the reaction involves a radical process.
基金the financial support from the National Natural Science Foundation of China(grant nos.22001117,21971108,21971111,and 21732003)the Natural Science Foundation of Jiangsu Province(grant no.BK20190006)+1 种基金Fundamental Research Funds for the Central Universities(0205/14380252),“Innovation&Entrepreneurship Talents Plan”of Jiangsu ProvinceFoundation of Advanced Catalytic Engineering Research Center of the Ministry of Education of Hunan University.
文摘Ketones serve as one of the most critical building blocks in organic synthesis,involving numerous functional group transformations.Herein,we rep ort an unprecedented photoredox-nickel metallap hotoredox-catalyzed decarboxylative acylation of common aliphatic acids with readily available aromatic and aliphatic thioesters.A wide range of structurally diverse asymmetrical aryl alkyl and dialkyl ketones have been constructed in yields of up to 98% with this strategy.The protocol has excellent reaction selectivity and functional group compatibility,representing a significant step forward in ketone synthesis.The one-pot decarboxylative acylation at the gram scale from two different carboxylic acids and the late-stage application for the synthesis of complex ketones shows its synthetic robustness.Both mechanistic experiments and density functional theory(DFT)calculations suggest that the decarboxylative acylation reaction operates via an underdeveloped Ni(Ⅰ)-Ni(Ⅱ)-Ni(Ⅰ)-Ni(Ⅲ)-Ni(Ⅰ)catalytic cycle.
