Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing c...Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing carbon dioxide as double synthons via bimolecular reduction remains challenging. Here, by leveraging the bimolecular reduction of carbon dioxide to carbonyl and methyl respectively, we describe a Pd-catalyzed trifunctionalization of alkynes with aryl iodide for the first time and showcase its advantages on the formation of various β-diketones and their application in the constructing of heterocyclic compounds with important biological activity, including pyrimidine, oxazole, pyrazole.展开更多
Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reductio...Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reduction was successfully applied to fulfill such a synthetic purpose.Due to our use of controllable electroreduction coupled with proton abstraction,we can report a room-temperature reductiveα-alkylation of the inert N-heteroarenes with abundantly available styrenes in an undivided Zn(+)/C(−)cell.This proceeds with good substrate compatibility and operational simplicity,utilizes cost-effective sacrificial Zn-anode,exhibits high selectivity,and does not need pressurized H2 gas and transition-metal catalysts.This current work offers a useful platform for direct construction of valuable aryl-fused 2-alkyl cyclic amines that are difficult to access with conventional methods.展开更多
Background and Originality Content As an inexpensive,fundamental and important feedstock for the petrochemical industry,methylarenes have long been regarded as one of the most widely used raw materials for a great var...Background and Originality Content As an inexpensive,fundamental and important feedstock for the petrochemical industry,methylarenes have long been regarded as one of the most widely used raw materials for a great variety of organic transformations.Therefore,the selective benzylic C(sp3)—H functionalization is particularly important,which provides a strategic means to utilize this resource.展开更多
A palladium-catalyzed regioselective three-component cascade reaction of carbon dioxide,amines and allenes has been developed,providing an expedient and practical method for the construction of a range of functionaliz...A palladium-catalyzed regioselective three-component cascade reaction of carbon dioxide,amines and allenes has been developed,providing an expedient and practical method for the construction of a range of functionalized carbamates containing dihydrobenzofuran or indole moiety in moderate to excellent yields.The broad substrate scope,good functional group tolerance and excellent chemo-and regioselectivity are the features of the transformation.展开更多
The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of(trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective...The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of(trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective strategy distinguishes the different nucleophilic heteroatom sites in amino alcohols and unsymmetric diamines by the sequential defluorinative functionalization of two C(sp^(3))–F bonds in a CF_(3) group. Various attractive monofluoroalkene-masked medium-sized heterocyclic lactams and lactones are obtained in moderate to excellent yields. Simple derivation of these masked-heterocycles efficiently affords useful skeletons of lactams, lactones, and 1,4-oxazepanes in a single diastereoisomer. Mechanism studies indicate that a unique sequential ipso-/γ-selective defluorinative functionalization pathway is involved in these transformations.展开更多
Herein, two efficient palladium-catalyzed intermolecular oxidative coupling reactions of (Z)-enamines with isocyanides via selective β-C(sp2)-H and/or C=C bond cleavage have been developed, leading to controllabl...Herein, two efficient palladium-catalyzed intermolecular oxidative coupling reactions of (Z)-enamines with isocyanides via selective β-C(sp2)-H and/or C=C bond cleavage have been developed, leading to controllable chemodivergent and stereoselective construction of a wide range of (E)-β-carbamoylenamine derivatives containing strong intramolecular hydrogen bonds. Furthermore, possible reaction pathways for these transfor- mations are proposed on the basis of preliminary mechanism studies.展开更多
By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroac...By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroacridines are efficiently transformed into the desired benzylic sulfonyl products via a radical/radical cross-coupling process,proceeding with the merits of broad substrate scope,operational simplicity,good functional group compatibility,and mild reaction conditions.展开更多
A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synth...A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.展开更多
We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild conditions.The act...We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild conditions.The activated group,CHZ(Z is electronwithdrawing group(EWG)),in the enyne substrates exerts two synergetic roles,one is to activate alkyne for the cyclopropanation reaction;the other is to introduce the C–H…O interaction between substrate and catalyst(reducing the energy barrier of the reaction).This double-mode activation was supported by both density functional theory(DFT)calculations and experimental tests.This strategy was also extended to other CH2 Z(Z can be OH,OMe,F)as activating groups that made the CH2 more acidic so that the substrates could also form increased C–H…O interaction with the catalyst.展开更多
The catalytic conversion of biomass-derived feedstocks into functional molecules is of significance to synthetic organic chemistry.Herein,through a palladium-catalyzed reductive annulation reaction of resorcinols and ...The catalytic conversion of biomass-derived feedstocks into functional molecules is of significance to synthetic organic chemistry.Herein,through a palladium-catalyzed reductive annulation reaction of resorcinols and 2-nitrobenzaldehydes,we present a new approach for the direct synthesis of acridinone derivatives,featuring operational simplicity,good substrate compatibility,and readily available feedstocks.展开更多
基金supported by the National Natural Science Foundation of China(21971073,22001075,22231002)the Natural Science Foundation of Guangdong Province(2019A1515011468)+2 种基金the Discipline Construction Project of Guangdong Medical University(4SG23231G,4SG23249G)the Ordinary University Characteristic Innovation Project of Guangdong Province(2022KTSCX047)the Key-Area Research and Development Program of Guangdong Province(2020B010188001)。
文摘Carbon dioxide reduction, as a sustainable and versatile strategy for the access of chemical fuels, has attracted increasing attention and enormous efforts have been devoted to it in recent years. However, employing carbon dioxide as double synthons via bimolecular reduction remains challenging. Here, by leveraging the bimolecular reduction of carbon dioxide to carbonyl and methyl respectively, we describe a Pd-catalyzed trifunctionalization of alkynes with aryl iodide for the first time and showcase its advantages on the formation of various β-diketones and their application in the constructing of heterocyclic compounds with important biological activity, including pyrimidine, oxazole, pyrazole.
基金support of the National Natural Science Foundation of China(grant no.21971071)the Natural Science Foundation of Guangdong Province(grant no.2021A1515010155).
文摘Despite their interesting applications,direct and diverse syntheses of aryl-fused 2-alkyl cyclic amines still remain challenging.Here,the concept of incorporating a C–C coupling process into the N-heteroaryl reduction was successfully applied to fulfill such a synthetic purpose.Due to our use of controllable electroreduction coupled with proton abstraction,we can report a room-temperature reductiveα-alkylation of the inert N-heteroarenes with abundantly available styrenes in an undivided Zn(+)/C(−)cell.This proceeds with good substrate compatibility and operational simplicity,utilizes cost-effective sacrificial Zn-anode,exhibits high selectivity,and does not need pressurized H2 gas and transition-metal catalysts.This current work offers a useful platform for direct construction of valuable aryl-fused 2-alkyl cyclic amines that are difficult to access with conventional methods.
基金The authors thank the National Key Research and Development Program of China(No.2016 YFA 0602900),the National Natural Science Foundation of Chin a(No.21420102003)Guangdong Province Science Foundation(No.2017 B 090903003)for financial support.
文摘Background and Originality Content As an inexpensive,fundamental and important feedstock for the petrochemical industry,methylarenes have long been regarded as one of the most widely used raw materials for a great variety of organic transformations.Therefore,the selective benzylic C(sp3)—H functionalization is particularly important,which provides a strategic means to utilize this resource.
基金supported by the Ministry of Science and Technology of China(2016YFA0602900)the National Natural Science Foundation of China(21971073,21572071)+2 种基金the Guangdong Natural Science Foundation(2019A1515011468,2017A030313054)China Postdoctoral Science Foundation(2018M640774)the Fundamental Research Funds for the Central Universities(D2191970).
文摘A palladium-catalyzed regioselective three-component cascade reaction of carbon dioxide,amines and allenes has been developed,providing an expedient and practical method for the construction of a range of functionalized carbamates containing dihydrobenzofuran or indole moiety in moderate to excellent yields.The broad substrate scope,good functional group tolerance and excellent chemo-and regioselectivity are the features of the transformation.
基金supported by the National Natural Science Foundation of China (21702064)the Guangdong Basic and Applied Basic Research Foundation (2020B1515020012)。
文摘The steric-switched ipso-defluoroamination-triggered and ipso-defluorooxylation-triggered cyclization of(trifluoromethyl)alkenes with amino alcohols and diamines are achieved under mild conditions. This regioselective strategy distinguishes the different nucleophilic heteroatom sites in amino alcohols and unsymmetric diamines by the sequential defluorinative functionalization of two C(sp^(3))–F bonds in a CF_(3) group. Various attractive monofluoroalkene-masked medium-sized heterocyclic lactams and lactones are obtained in moderate to excellent yields. Simple derivation of these masked-heterocycles efficiently affords useful skeletons of lactams, lactones, and 1,4-oxazepanes in a single diastereoisomer. Mechanism studies indicate that a unique sequential ipso-/γ-selective defluorinative functionalization pathway is involved in these transformations.
基金The authors thank the National Key Research and Development Program of China (2016YFA0602900) and the National Natural Science Foundation of China (21490572 and 21420102003) for financial support.
文摘Herein, two efficient palladium-catalyzed intermolecular oxidative coupling reactions of (Z)-enamines with isocyanides via selective β-C(sp2)-H and/or C=C bond cleavage have been developed, leading to controllable chemodivergent and stereoselective construction of a wide range of (E)-β-carbamoylenamine derivatives containing strong intramolecular hydrogen bonds. Furthermore, possible reaction pathways for these transfor- mations are proposed on the basis of preliminary mechanism studies.
基金the National Natural Science Foundation of China(No.21971071)the Natural Science Foundation of Guangdong Province(No.2021A1515010155)the Fundamental Research Funds for the Central Universities(No.2020ZYGXZR075).
文摘By employing a readily available CuCI/DDQ catalyst system,we herein report a direct C(sp^(3))-H sulfonylation of xanthene derivates with odorless sodium sulfinates.Various 9H-xanthenes,thioxanthenes,and 9,10-dihydroacridines are efficiently transformed into the desired benzylic sulfonyl products via a radical/radical cross-coupling process,proceeding with the merits of broad substrate scope,operational simplicity,good functional group compatibility,and mild reaction conditions.
文摘A silver-catalyzed three-component coupling reaction of carbon dioxide, amines and α-diazoesters has been developed for the first time. The novel reaction provides an efficient and practical methodology for the synthesis of a wide range of new α-carbamoyloxy esters, which are difficult to prepare by existing methods. The advantages of the method include the use of readily available starting materials, simple catalytic system, good atom economy and high functional group tolerance.
基金the National Natural Science Foundation of China(2187109621672071+7 种基金91856105)the Ministry of Science and Technology of China(2016YFA0602900)the Natural Science Foundation of Guangdong(2018B0303080072018A0303103592016A030310433)the Science and Technology Program of Guangzhou(201707010316)the Fundamental Research Funds for the Central UniversitiesSouth China University of Technology。
文摘We report the first Rh2(II)-catalyzed asymmetric cycloisomerization of activated enynes to provide cyclopropane-fused tetrahydropyridines in good yields and excellent enantioselectivities under mild conditions.The activated group,CHZ(Z is electronwithdrawing group(EWG)),in the enyne substrates exerts two synergetic roles,one is to activate alkyne for the cyclopropanation reaction;the other is to introduce the C–H…O interaction between substrate and catalyst(reducing the energy barrier of the reaction).This double-mode activation was supported by both density functional theory(DFT)calculations and experimental tests.This strategy was also extended to other CH2 Z(Z can be OH,OMe,F)as activating groups that made the CH2 more acidic so that the substrates could also form increased C–H…O interaction with the catalyst.
基金We thank the National Natural Science Foundation of China(21971071)the Natural Science Foundation of Guangdong Province(2021A1515010155 and 2019B090905007)the Fundamental Research Funds for the Central Universities(2020ZYGXZR075)for financial support.
文摘The catalytic conversion of biomass-derived feedstocks into functional molecules is of significance to synthetic organic chemistry.Herein,through a palladium-catalyzed reductive annulation reaction of resorcinols and 2-nitrobenzaldehydes,we present a new approach for the direct synthesis of acridinone derivatives,featuring operational simplicity,good substrate compatibility,and readily available feedstocks.