Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, d...Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.展开更多
The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still rema...The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still remains challenging yet highly desirable until now.Herein,we report a novel formal[3+3]cascade cyclization reaction to provide lactam-fused 4-fluoroalkylated 3,4-dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis.Of note,these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp^(2))-Cl and C(sp^(3))-H functionalization,which exhibited highly site-selectivity and stereoselectivity.Additionally,evaluations on biological activities of the obtained products revealed that several products display inhibitory activity against Siha and H1975 cancer cell lines.展开更多
Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copp...Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copper catalysis and photocatalysis is reported,allowing the construction of chiral 5-((sulfonyl)methyl)dihydrofuran-2(3H)-ones with β-quaternary stereocenters.During the transformation,sodium hydrogen sulfite is used as the sulfur dioxide surrogate.Excellent enantiocontrol(up to 99%ee)and wide functional group compatibility are observed in this asymmetric radical sulfonylation.展开更多
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron tran...The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.展开更多
The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasoni...The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.展开更多
Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashi...Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.展开更多
A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHP...A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.展开更多
An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-st...An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives.Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer(LMCT)/1,4-hydrogen atom transfer(HAT)cascade.展开更多
Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive fun...Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive functional group compatibility.This strategy represents a significant advance in copper-catalyzed carbonylation involving alkyl bromides and C(sp2)-nucleophiles.The protocol addresses key challenges commonly encountered in the coupling of C(sp3)-alkyl halides with aryl boron reagents,such as sluggish oxidative addition of alkyl halides,competing Suzuki-Miyaura cross-coupling,undesired dehalogenation and so on.Distinguished by its broad substrate scope and high functional group tolerance,this approach offers a robust and versatile platform for the streamlined synthesis of alkyl aryl ketones.展开更多
An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones a...An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.展开更多
Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes th...Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.展开更多
A catalytic method was developed to synthesize substituted phenols from the corresponding aryl bromides and chlorides under mild conditions （yields = 34-92%）. 4-Methoxylbenzyl alcohol was used as water surrogate and...A catalytic method was developed to synthesize substituted phenols from the corresponding aryl bromides and chlorides under mild conditions （yields = 34-92%）. 4-Methoxylbenzyl alcohol was used as water surrogate and CuI/3,4,7,8-tetramethyl-1,10- phenanthroline was used as catalyst to achieve the C-O cross-coupling.展开更多
Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably...Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.展开更多
Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivi...Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivity.CuBr-Dppp combination gives the best outcomes.The substrate scope is profiled.展开更多
A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were syn...A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.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
Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Her...Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.展开更多
We examined the puzzling mechanism for Cu-catalyzed meta-C-H arylation reaction of anilides by diaryliodonium salts through systematic theoretical analysis. The previously proposed anti-oxy-cupration mechanism featuri...We examined the puzzling mechanism for Cu-catalyzed meta-C-H arylation reaction of anilides by diaryliodonium salts through systematic theoretical analysis. The previously proposed anti-oxy-cupration mechanism featuring anti-1,2- or anti-1,4-addition of cuprate and oxygen to the phenyl ring generating a meta-cuprated intermediate was excluded due to the large activation barriers. Alternatively, a new amide-directed carbocupration mechanism was proposed which involves a critical rate- and regio-determining step of amide-directed addition of the Cu（III）-aryl bond across the phenyl C2=C3 double bond to form an orthocuprated, meta-arylated intermediate. This mechanism is kinetically the most favored among several possible mechanisms such as ortho-or para-cupration/migration mechanism, direct meta C-H bond cleavage mediated by Cu（III） or Cu（I）, and Cu（III）-catalyzed ortho-directed C-H bond activation mechanism this mechanism has been shown to Furthermore, the predicted regioselectivity based on favor the meta-arylation that is consistent with the experimental observations.展开更多
Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and...Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and 2-hydroxydihydrofuran-3(2H)-one(HDFO)products with high levels of stereoselectivity under identical conditions.The protocol features the use of earth-abundant copper catalyst,mild conditions,shortening synthetic routes in constructing different molecular frameworks,and reducing the corresponding possible waste production.The substituents of the nucleophilicα-diketones play crucial roles in switching the reaction pathways.展开更多
A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand e...A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand enantioselectivities.In this reaction,the kinetic resolution of HP(S)ROR'occurs,which affords(R)-HP(S)Ph OMe in high enantioselectivity in the addition with(R,R)-Ph-BPE as the ligand.It is found through control experiment that dual“soft-soft”interaction,indicated by both1H and31P NMR experiments,is indispensable in the present reaction.The first“soft-soft”interaction between copper(Ⅰ)catalyst and HP(S)ROR'enables facile deprotonation to generate nucleophilic[Cu]-SPROR'species.The second one between the[Cu]-SPROR'species andα,β-unsaturated thioamides facilitated the nucleophilic addition.Finally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.展开更多
文摘Visible light photocatalytic redox catalysis has become a powerful tool for organic synthesis, and has opened up new avenues for the formation of challenging structural skeletons and chemical bonds. In this respect, diverse photocatalysts, including ruthenium(II), iridium(Ⅲ), and organic dyes, have been most commonly applied.
基金the Talents Program of Guangdong Province(2023QN10Y314)Guangdong Basic and Applied Basic Research Foundation(2024A151501212,2023A1515012657)+3 种基金Zhanjiang Ocean Young Talent Innovation Project(2023E0002)The Research Fund of Talents Program of Guangdong Medical University(4RS23002d4SG24248G)The Cultivating Research Fund of Guangdong Medical University(2XJ24006)。
文摘The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4-dihydro-2H-pyran architectures.Nevertheless,the transformation for preparing fused-polycyclic ones still remains challenging yet highly desirable until now.Herein,we report a novel formal[3+3]cascade cyclization reaction to provide lactam-fused 4-fluoroalkylated 3,4-dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis.Of note,these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp^(2))-Cl and C(sp^(3))-H functionalization,which exhibited highly site-selectivity and stereoselectivity.Additionally,evaluations on biological activities of the obtained products revealed that several products display inhibitory activity against Siha and H1975 cancer cell lines.
基金supported by the National Natural Science Foundation of China(22171206)the Natural Science Foundation of Zhejiang Province(LZ23B020001)the Zhejiang Provincial Ten Thousand Talent Program(2023R5244)。
文摘Enantioselective intramolecular radical difunctionalization of alkenes involving sulfur dioxide through a three-component reaction of 4-arylpent-4-enoic acids,sodium hydrogen sulfite and thianthrenium salts under copper catalysis and photocatalysis is reported,allowing the construction of chiral 5-((sulfonyl)methyl)dihydrofuran-2(3H)-ones with β-quaternary stereocenters.During the transformation,sodium hydrogen sulfite is used as the sulfur dioxide surrogate.Excellent enantiocontrol(up to 99%ee)and wide functional group compatibility are observed in this asymmetric radical sulfonylation.
基金supported by the National Natural Science Foundation of China (No.22271166)the Frontiers Science Center for New Organic Matter,Nankai University (No.63181206) for generous financial support for our programs。
文摘The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals,where electron transfer at the electrode produces catalysts with more valence states.Among these transition metal catalysts,electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention.This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates,which can be broadly classified into the functionalization of C=C bonds,C-H bond activation,C-C and C-X bond activation,and so on.
基金supported by Yunnan Major Scientific and Technological Projects(Grant No.202402AB080004)Yunnan Provincial Education Department Universities Serve Key Industry Science and Technology Projects(Grant No:FWCY-BSPY2024043)+1 种基金Top Innovative Talents for Graduate Students of KUST(Grant No:CA24163M116A)Analysis and Testing Fund of KUST(Grant No:2024P20233102006).The authors extend their gratitude to Mr.Kong Qingyuan from Scientific Compass(www.shiyanjia.com)for providing invaluable assistance with scientific research.
文摘The accumulation of refractory organics in Bayer liquor(pH 14.4)critically compromises aluminum production efficiency and product quality,necessitating sustainable remediation strategies.Herein,we develop an ultrasonic-driven catalytic ozonation system with dynamically reconstructed CuO/Cu2O heterointerfaces,achieving unprecedented efficiency in extreme alkaline wastewater treatment.Atomic-scale interface engineering endows the catalyst with hydrophilicity(contact angle:6.1°)and 3.8–4.3 times higher oxygen vacancy density compared to single-phase catalysts.These properties facilitate efficient interfacial interactions with Bayer liquor and enable superior ozone activation through synergistic Cu(I)/Cu(II)redox cycling across the heterointerface.This interfacial synergy reduces ozone adsorption energy from 5.46 eV(Cu_(2)O)to 1.48 eV,driving the generation of reactive oxygen species(ROS)via low-energy pathways.Under optimized conditions,the system achieves 57.82%TOC removal within 1.5 h with 2.3-fold faster kinetics than ozone–alone processes,while improving energy efficiency by 1.82–3.22 times per kWh over conventional thermal oxidation.Remarkable stability is demonstrated through 80.21%activity retention after 6 cycles,attributed to surface energy minimization(0.61 J m^(−2)),alongside 67.91%hydroxyl radical(•OH)-mediated degradation confirmed by quenching tests.In XPS,EEMs analysis,and ECOSAR modeling further elucidate the surface reconstruction mechanism and intermediate toxicity reduction.This work establishes an atomic interface design paradigm that bridges catalytic innovation with green metallurgy applications,offering a sustainable solution for industrial wastewater remediation aligned with circular economy principles.
基金supported by the National Natural Science Foundation of China(22271170)the Scientific Research Foundation of Qingdao University of Science and Technology(1203043003457).
文摘Internal alkynes are widespread skeletons in bioactive molecules and materials which are also used as important building blocks in chemical synthesis. Herein, we report a novel and efficient copper-catalyzed Sonogashira reaction between sulfonium salts and alkynes through an anti-Markovnikov ring-opening pathway promoted by visible light. The coexistence of the nitrogen and phosphorus ligands in the system is the key to the success of this reaction. This radical type ring-opening reaction affords a new strategy for the synthesis of internal alkynes. Furthermore, this study is also an effective complement to the diverse reaction patterns of sulfonium salts.
基金supported by the National Natural Science Foundation of China(22201087)the National Key R&D Program of China(2022YFA1503200)Guangdong Basic and Applied Basic Research Foundation(2022A1515012507)。
文摘A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.
基金support from the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province(No.UNPYSCT-2017124).
文摘An atom economicβ-C(sp^(3))−H chlorination of amide derivatives has been developed.This mild protocol employs CuCl_(2) instead of palladium catalysts with atom-economic HCl as chlorine sources and enables the late-stage functionalization of medicine derivatives.Mechanism studies suggest a plausible visible light triggered ligand-to-metal charge transfer(LMCT)/1,4-hydrogen atom transfer(HAT)cascade.
文摘Herein,we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp3)-C(sp2)ketones with extensive functional group compatibility.This strategy represents a significant advance in copper-catalyzed carbonylation involving alkyl bromides and C(sp2)-nucleophiles.The protocol addresses key challenges commonly encountered in the coupling of C(sp3)-alkyl halides with aryl boron reagents,such as sluggish oxidative addition of alkyl halides,competing Suzuki-Miyaura cross-coupling,undesired dehalogenation and so on.Distinguished by its broad substrate scope and high functional group tolerance,this approach offers a robust and versatile platform for the streamlined synthesis of alkyl aryl ketones.
基金financial support from the National Natural Science Foundation of China (Nos. 21801087 and 22201089)。
文摘An enantioselective catalytic method for the direct [4 + 1] annulation of yne–allylic acetates with pyrazolones has been realized by a copper-catalyzed remote strategy. A variety of enantioenriched spiropyrazolones are rapidly accessed in high yields with moderate to good enantiocontrol. The facile follow-up transformations highlight its potential utility in the synthesis of diverse spiropyrazolones building blocks.
基金the National Natural Science Foundation of China (Nos. 2127222, 21432009, 21472177, J1310010)Chinese Academy of Sciences(No. XDB20000000)
文摘Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.
基金the Six Kinds of Professional Elite Foundation of Jiangsu Province(No.07-A-024)the Natural Science Foundation of Jiangsu Education Department(No.08KJB 150002)the Natural Science Foundation of Huaihai Institute of Technology(No.Z2008024) for financial support
文摘A catalytic method was developed to synthesize substituted phenols from the corresponding aryl bromides and chlorides under mild conditions （yields = 34-92%）. 4-Methoxylbenzyl alcohol was used as water surrogate and CuI/3,4,7,8-tetramethyl-1,10- phenanthroline was used as catalyst to achieve the C-O cross-coupling.
基金supported by National Natural Science Foundation of China(21672119)China Postdoctoral Science Foundation(2018M641624)~~
文摘Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.
基金the National Natural Science Foundation of China(No.21672027)for financial supportsupported by High-Level Entrepreneurial Talent Team of Jiangsu Province(No.2017-37)。
文摘Borylative cyclization of E-3-arylallyl carbamoyl chlorides is achieved through copper catalyzed intramolecular carboboration with B_(2)pin_(2).2-Aryl-3-boryl-γ-lactams are formed with exclusive cisdiastereoselectivity.CuBr-Dppp combination gives the best outcomes.The substrate scope is profiled.
基金Financial support from the National Natural Science Foundation of China(Nos.21971201,22171220)the Fundamental Research Funds of the Central Universities(No.xtr072022003)。
文摘A photoinduced copper-catalyzed alkoxyl triggered C-C bond cleavage/aminocarbonylation cascade is presented.Through adjusting the structure of alkoxyl radical precursors,functionalized lactones and ketoamides were synthesized with good yields and excellent functional group tolerance under redox-neutral conditions.Notably,this protocol enables the integration of lactone fragments with many amine drugs and drug fragments.
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financial support from the National Natural Science Foundation of China (No.21801087)Fundamental Research Funds for the Central Universities CCNU (No.CCNU19QN064)+2 种基金the Ministry of Science and Technology of China (No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists (No.GZS2020001)the Key Scientific and Technological Project of Henan Province (No.212102311068)。
文摘Anthrones are key structural motifs in many natural products, bioactive compounds and pharmaceutical chemicals. Earth-abundant-metal-catalyzed asymmetric functionalization of anthrones has not proved to be viable. Herein, we disclosed a highly enantioselective propargylic substitution of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand. This strategy is amenable to a broad range of substrates, uses readily available starting materials, provides excellent yields with remarkable enantioselectivity under mild conditions, and enables attractive products diversification routes.
基金This work was supported by the National Natural Science Foundation of China （No.20971058） and the Fundamental Research Funds for the Central Universities （No.JUSRPIII05）.
文摘We examined the puzzling mechanism for Cu-catalyzed meta-C-H arylation reaction of anilides by diaryliodonium salts through systematic theoretical analysis. The previously proposed anti-oxy-cupration mechanism featuring anti-1,2- or anti-1,4-addition of cuprate and oxygen to the phenyl ring generating a meta-cuprated intermediate was excluded due to the large activation barriers. Alternatively, a new amide-directed carbocupration mechanism was proposed which involves a critical rate- and regio-determining step of amide-directed addition of the Cu（III）-aryl bond across the phenyl C2=C3 double bond to form an orthocuprated, meta-arylated intermediate. This mechanism is kinetically the most favored among several possible mechanisms such as ortho-or para-cupration/migration mechanism, direct meta C-H bond cleavage mediated by Cu（III） or Cu（I）, and Cu（III）-catalyzed ortho-directed C-H bond activation mechanism this mechanism has been shown to Furthermore, the predicted regioselectivity based on favor the meta-arylation that is consistent with the experimental observations.
基金the National Natural Science Foundation of China(Nos.22071242 and 21871260)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)+1 种基金Fujian Natural Science Foundation(No.2018J05035)Science and Technology Research Program of the Education Department of Jiangxi Province(No.GJJ1991151)。
文摘Copper-catalyzed divergent annulations betweenα-diketones and alkynylα-diketones have been achieved,delivering a series of highly functionalized and biologically important cis-hexahydro-2Hcyclopenta[b]furan(HCPF)and 2-hydroxydihydrofuran-3(2H)-one(HDFO)products with high levels of stereoselectivity under identical conditions.The protocol features the use of earth-abundant copper catalyst,mild conditions,shortening synthetic routes in constructing different molecular frameworks,and reducing the corresponding possible waste production.The substituents of the nucleophilicα-diketones play crucial roles in switching the reaction pathways.
基金the financial support from the National Natural Science Foundation of China(No.22271302)the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417100 and 21XD1424800)+1 种基金CAS Key Laboratory of Synthetic Chemistry of Natural SubstancesShanghai Institute of Organic Chemistry。
文摘A copper(Ⅰ)-catalyzed diastereodivergent addition of phosphinothioates(HP(S)ROR')toα,β-unsaturated thioamides is disclosed,which constructs vicinal P-chiral and C-chiral centers in generally high diastereoand enantioselectivities.In this reaction,the kinetic resolution of HP(S)ROR'occurs,which affords(R)-HP(S)Ph OMe in high enantioselectivity in the addition with(R,R)-Ph-BPE as the ligand.It is found through control experiment that dual“soft-soft”interaction,indicated by both1H and31P NMR experiments,is indispensable in the present reaction.The first“soft-soft”interaction between copper(Ⅰ)catalyst and HP(S)ROR'enables facile deprotonation to generate nucleophilic[Cu]-SPROR'species.The second one between the[Cu]-SPROR'species andα,β-unsaturated thioamides facilitated the nucleophilic addition.Finally,both Michael adducts and(R)-HP(S)PhOMe are easily converted to synthetically useful compounds.
