A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatal...A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatalysis enables two types of acylation of unsaturated hydrocarbons by adjusting the categories of acyl radical precursors.Aroyl chlorides as bifunctional reagents react with 1,6-enynes to realize annulative chloroacylation,while acyl oxime esters are used as acyl radical precursors,which undergo a three-component annulative alkoxyacylation by treatment with 1,6-enynes and alcohols.The current method demonstrates good functional group compatibility,a broad substrate scope and mild reaction conditions.展开更多
The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic comp...The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.展开更多
A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regiosel...A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaf-fold,namely,benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles,in good to excellent yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and high regioselectivity,providing a catalytic and flexible method for creating bridged aryl-indole skeletons.展开更多
A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreport...A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.展开更多
Indoles and their derivatives are an important class of N-heterocycles.In this article,iridium-catalyzed annulation reactions of N-aryl-2-aminopyridines to synthesize indole derivatives are designed and developed,whic...Indoles and their derivatives are an important class of N-heterocycles.In this article,iridium-catalyzed annulation reactions of N-aryl-2-aminopyridines to synthesize indole derivatives are designed and developed,which utilize vinylene carbonate as a new C2 synthon.This protocol is expected to provide a facile and useful access to various indole derivatives.展开更多
A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)...A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.展开更多
A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yiel...A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β’-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate.Moreover,this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.展开更多
Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrifici...Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrificial approach.The catalyst demonstrated a broad substrate scope and good functional group tolerance,achieving yields of up to 84%.Additionally,the catalyst exhibited reusability and can be recycled up to three times.The CoP@N–C-1.5 was characterized using X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The results indicated that the catalyst contained Co2P nanoparticles.The X-ray photoelectron spectroscopy(XPS)further confirms the presence of Co-P.Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co_(2)P nanoparticles.展开更多
Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has...Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has seen remarkable progress in recent years.Among the various synthetic methodologies for accessing chromone scaffolds,the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy.This approach,through direct vinyl C-H bond functionalization of o-hydroxyaryl enaminones,enables the construction of structurally diverse chromones(including 3-substituted chromones,2-substituted chromones,and 2,3-disubstituted chromones)and their derivatives since mid-2019.In this review,we highlight recent advances in the synthesis of various types of chromones and their derivatives,achieved through tandem direct vinyl C-H activation and chromone annulation of o-hydroxyaryl enaminones.展开更多
A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regiosel...A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and complete regioselectivity,providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.展开更多
Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the ...Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.展开更多
Rhodium(III)-catalyzed coupling between ketoximes and alkynes via C–H activation and annulation typically followed the[4+2]selectivity to afford isoquinolines.By designing alkynes bearing a highly electron-withdrawin...Rhodium(III)-catalyzed coupling between ketoximes and alkynes via C–H activation and annulation typically followed the[4+2]selectivity to afford isoquinolines.By designing alkynes bearing a highly electron-withdrawing group and under substrate control,we have successfully switched the selectivity of the coupling between oximes and alkynes to the alternative[3+2]annulation,leading to the efficient synthesis of indenamines.This process features good regioselectivity for both substrates,high efficiency,broad substrate scope,and excellent functional group tolerance.展开更多
A novel asymmetric[4+2]cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidonederived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-cata...A novel asymmetric[4+2]cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidonederived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-catalysis.An array of enantioenriched spiro-pyrrolidine-2,3-diones bearing adjacent quaternary and tertiary stereocenters are obtained in high yields with excellent enantioselectivities(up to 96% yield and 99% ee).The further transformation of the product has been accomplished for the construction of medical interesting β^(2,2)-amino acids and β-lactams.Preliminary mechanistic research was well conducted.展开更多
Rhodium-catalyzed C4aryl-H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed.These novel sa...Rhodium-catalyzed C4aryl-H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed.These novel salts serve as new full-color emissive fluorophores(433-633 nm),just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring.Furthermore,these salts can undergo ring-opening C5_(aryl)-H activation/annulation with a different alkyne to form non-symmetric and AIE-active1,1-biisoquinolines,where NH_(4)OAc plays an indispensable role that accounts for Hofmann elimination and imine formation,leading to an unprecedented imine dance:cyclic imine→N-alkenyl imine→NH imine.The15N labelling experiments indicate that the 2ndannulation includes two pathways:N-exchange(major)and N-retention(minor).展开更多
A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step econ...A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).展开更多
A[4+4]annulation reaction for the construction of medium-sized N-heterocycles is reported.This process involves the generation of all-carbon 1,4-dipoles containing aπ-allylpalladium complex from Morita-Baylis-Hillman...A[4+4]annulation reaction for the construction of medium-sized N-heterocycles is reported.This process involves the generation of all-carbon 1,4-dipoles containing aπ-allylpalladium complex from Morita-Baylis-Hillman(MBH)carbonates under the catalysis of Pd/Synphos,which then undergo Michael addition/N-allylic alkylation with 1-azadienes.A spectrum of eight-membered N-heterocycles featuring a trisubstituted exo-cyclic double bond is furnished efficiently with moderate to good E/Z selectivity and moderate atroposelectivity.In addition,moderate enantioselectivity can be realized by using a chiral ligand or with the assistant of a chiral quaternary ammonium salt.展开更多
An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a...An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a simple synthetic method for N-aryl indoles.展开更多
Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of ...Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of sustainable chemistry,the first-row transition metals,such as Mn,Fe,Co,Ni and Cu,have been recognized as cheap,environmentally friendly and reactively effective catalysts for a number of C-H functionalization reactions.However,compared with the commonly used alkenes and alkynes in the first-row transition-metal-catalyzed C–H activations,considerable achievements have just been made by the use of structurally unique and reactively rich allenes as coupling partners in recent years.This review summarizes the recent progress of the first-row transition-metal-catalyzed C–H activations with allenes.展开更多
Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselec...Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselectivity,providing a facile and efficient approach to access a variety of 2-aminothiazole derivatives with good functional groups tolerance.展开更多
文摘A new photocatalytic annulative acylative difunctionalization of 1,6-enynes is reported,enabling stereoselective access to acylated 1-indanones with cyclic quaternary centers in moderate to good yields.This photocatalysis enables two types of acylation of unsaturated hydrocarbons by adjusting the categories of acyl radical precursors.Aroyl chlorides as bifunctional reagents react with 1,6-enynes to realize annulative chloroacylation,while acyl oxime esters are used as acyl radical precursors,which undergo a three-component annulative alkoxyacylation by treatment with 1,6-enynes and alcohols.The current method demonstrates good functional group compatibility,a broad substrate scope and mild reaction conditions.
文摘The Rh(III)-catalyzed C—H functionalization of sulfoxonium ylides and successively annulation with two classes of cyclic diazo compounds has been realized,affording structurally diverse fused-ring or spirocyclic compounds under redoxneutral conditions.The reaction proceeds via successive chelation-assisted C—H activation,carbene insertion,and intramolecular[3+3]/[4+1]annulation processes.
基金the National Natural Science Foundation of China(Nos.21971090 and 22271123).
文摘A new palladium-catalyzed annulative allylic alkylation(AAA)reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described,leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaf-fold,namely,benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles,in good to excellent yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and high regioselectivity,providing a catalytic and flexible method for creating bridged aryl-indole skeletons.
基金financial support from the schoollevel research projects of Yancheng Institute of Technology(No.xjr2020044)the National Natural Science Foundation of China(Nos.22101151 and 21971090)。
文摘A new Rh(Ⅲ)-catalyzed aldehydic C-H activation/[4+3]annulation cascade of N-sulfonyl-2-aminobenzaldehydes with gem-difluorocyclopropenes is reported for the first time,and used to produce a range of hitherto unreported precedentedβ-monofluorinated benzo[b]azepin-5-ones with good yields and complete regioselectivity.This approach features a broad substrate scope,good functional group tolerance,and high regioselectivity,which may include Rh(Ⅲ)-catalyzed aldehydic C-H activation,tandem site-/regioselective insertion,defluorinated ring-scission,and 1,2-elimination.
文摘Indoles and their derivatives are an important class of N-heterocycles.In this article,iridium-catalyzed annulation reactions of N-aryl-2-aminopyridines to synthesize indole derivatives are designed and developed,which utilize vinylene carbonate as a new C2 synthon.This protocol is expected to provide a facile and useful access to various indole derivatives.
文摘A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.
基金financially supported by the National Natural Science Foundation of China(No.21572271).
文摘A[3+4]annulation of α-substituted allenes and Schiff bases is reported.This methodology serves as a conduit for the construction of a series of biologically important benzazepine derivatives in good to excellent yields under mild conditions by an unprecedented mode involving β’-carbon of α-substituted allenes and the proposed mechanism is supported by capturing the intermediate.Moreover,this class of benzazepine derivatives exhibited potential ability of cytotoxicity toward cancer cells.
基金support from the National Natural Science Foundation of China(Nos.22061017 and21862006)the Science and Technology program of Gansu Province(Nos.22YF7GG127 and 23JRRG0002)+1 种基金National innovative training program for college students(No.202310740015)the Open Project Funding of Hubei Key Laboratory of Processing and Application of Catalytic materials(No.202306004)。
文摘Designing efficient,recyclable,and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives.In this context,a novel N-stable Co_(2)P nano-catalyst(CoP@N–C-1.5)was developed using a templatesacrificial approach.The catalyst demonstrated a broad substrate scope and good functional group tolerance,achieving yields of up to 84%.Additionally,the catalyst exhibited reusability and can be recycled up to three times.The CoP@N–C-1.5 was characterized using X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The results indicated that the catalyst contained Co2P nanoparticles.The X-ray photoelectron spectroscopy(XPS)further confirms the presence of Co-P.Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co_(2)P nanoparticles.
基金financially supported by National Natural Science Foundation of China(No.22161022).
文摘Chromones serve as versatile heterocyclic scaffolds and are common core structural units in a variety of natural products and bioactive organic molecules.This area of research,at the forefront of organic synthesis,has seen remarkable progress in recent years.Among the various synthetic methodologies for accessing chromone scaffolds,the tandem annulation of o-hydroxyaryl enaminones has emerged as a robust and practical strategy.This approach,through direct vinyl C-H bond functionalization of o-hydroxyaryl enaminones,enables the construction of structurally diverse chromones(including 3-substituted chromones,2-substituted chromones,and 2,3-disubstituted chromones)and their derivatives since mid-2019.In this review,we highlight recent advances in the synthesis of various types of chromones and their derivatives,achieved through tandem direct vinyl C-H activation and chromone annulation of o-hydroxyaryl enaminones.
基金National Natural Science Foundation of China(Nos.21971090 and 22271123)the NSF of Jiangsu Province(No.BK20230201)+1 种基金the Natural Science Foundation of Jiangsu Education Committee(No.22KJB150024)the Natural Science Foundation of Jiangsu Normal University(No.21XSRX010)。
文摘A new oxidative N-heterocyclic carbene(NHC)-catalyzed high-order[7+3]annulation reaction ofγ-indolyl phenols as 1,7-dinucleophiles andα,β-alkynals with the aid of Sc(OTf)_(3)is reported,enabling the highly regioselective access to unprecedented polyarene-fused ten-membered lactams bearing a bridged aryl-aryl-indole scaffold in moderate to good yields.This protocol demonstrates a broad substrate scope,good compatibility with substituents and complete regioselectivity,providing an organocatalytic modular synthetic strategy for creating medium-sized lactams.
基金the National Natural Science Foundation of China(Nos.22171147 and 21871148)for the financial support。
文摘Polycyclic compounds are widely found in natural products and drug molecules with important biological activities,which attracted the attention of many chemists.Phosphine-catalyzed nucleophilic addition is one of the most powerful tools for the construction of various cyclic compounds with the advantages of atom economy,mild reaction conditions and simplicity of operation.Allenolates,Morita−Baylis−Hillman(MBH)alcohols and their derivatives(MBHADs),electron-deficient olefins and alkynes are very efficient substrates in phosphine mediated annulations,which formed many phosphonium species such asβ-phosphonium enolates,β-phosphonium dienolates and vinyl phosphonium ylides as intermediates.This review describes the reactivities of these phosphonium zwitterions and summarizes the synthesis of polycycle compounds through phosphine-mediated intramolecular and intermolecular sequential annulations.Thus,a systematic summary of the research process based on the phosphine-mediated sequential annulations of allenolates,MBH alcohols and MBHADs,electron-deficient olefins and alkynes are presented in Chapters 2-6,respectively.
基金supported by the Dalian Institute of Chemical Physics,Chinese Academy of Sciencesthe National Natural Science Foundation of China(21472186,21272231)
文摘Rhodium(III)-catalyzed coupling between ketoximes and alkynes via C–H activation and annulation typically followed the[4+2]selectivity to afford isoquinolines.By designing alkynes bearing a highly electron-withdrawing group and under substrate control,we have successfully switched the selectivity of the coupling between oximes and alkynes to the alternative[3+2]annulation,leading to the efficient synthesis of indenamines.This process features good regioselectivity for both substrates,high efficiency,broad substrate scope,and excellent functional group tolerance.
基金Financial support from the National Key Research and Development Program of China(No.2021YFF0600704)。
文摘A novel asymmetric[4+2]cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidonederived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-catalysis.An array of enantioenriched spiro-pyrrolidine-2,3-diones bearing adjacent quaternary and tertiary stereocenters are obtained in high yields with excellent enantioselectivities(up to 96% yield and 99% ee).The further transformation of the product has been accomplished for the construction of medical interesting β^(2,2)-amino acids and β-lactams.Preliminary mechanistic research was well conducted.
基金financial support from the National Natural Science Foundation of China(Nos.22261013 and 22001049)Guangxi Natural Science Foundation(No.2020GXNSFBA297003)Magneto-Chemical Functional Materials(No.EMFM20221102)。
文摘Rhodium-catalyzed C4aryl-H activation and ring-retentive annulation of 2H-imidazoles with internal alkynes to build imidazo[5,1-a]isoquinolinium salts with high yields and broad scope has been disclosed.These novel salts serve as new full-color emissive fluorophores(433-633 nm),just by simply modifying the substituents on C3 and C4 positions of isoquinoline ring.Furthermore,these salts can undergo ring-opening C5_(aryl)-H activation/annulation with a different alkyne to form non-symmetric and AIE-active1,1-biisoquinolines,where NH_(4)OAc plays an indispensable role that accounts for Hofmann elimination and imine formation,leading to an unprecedented imine dance:cyclic imine→N-alkenyl imine→NH imine.The15N labelling experiments indicate that the 2ndannulation includes two pathways:N-exchange(major)and N-retention(minor).
文摘A[Cp*RhCl_(2)]_(2)-catalyzed intramolecular annulation reaction via aminoalkylation of alkenes with diazo compounds has been developed to construct highly-functionalized isoindolinones.This approach exhibits step economy,mild reaction conditions,and good functional group tolerance,facilitating access to a wide range of highly-valuable functionalized isoindolinones with high level of yields(up to 99%yield).
文摘A[4+4]annulation reaction for the construction of medium-sized N-heterocycles is reported.This process involves the generation of all-carbon 1,4-dipoles containing aπ-allylpalladium complex from Morita-Baylis-Hillman(MBH)carbonates under the catalysis of Pd/Synphos,which then undergo Michael addition/N-allylic alkylation with 1-azadienes.A spectrum of eight-membered N-heterocycles featuring a trisubstituted exo-cyclic double bond is furnished efficiently with moderate to good E/Z selectivity and moderate atroposelectivity.In addition,moderate enantioselectivity can be realized by using a chiral ligand or with the assistant of a chiral quaternary ammonium salt.
基金supported by the Intercollegiate Key Scientific Research Projects of Henan Province(15A150018)~~
文摘An efficient Cu catalyzed selective arylation/annulation cascade reaction of 2-alkynylanilines with diaryliodonium salts was developed.This reaction was selective to N-arylation instead of C-arylation,which provides a simple synthetic method for N-aryl indoles.
基金support of this work by the National Natural Science Foundation of China (No. 21502242)the State Key Laboratory of Natural and Biomimetic Drugs (No. K20150215)
文摘Transition-metal-catalyzed C–H activation reaction has proven to be a powerful and efficient tool for the formation of diverse C-C and C–X bond and construction of functional complex molecules.From the viewpoint of sustainable chemistry,the first-row transition metals,such as Mn,Fe,Co,Ni and Cu,have been recognized as cheap,environmentally friendly and reactively effective catalysts for a number of C-H functionalization reactions.However,compared with the commonly used alkenes and alkynes in the first-row transition-metal-catalyzed C–H activations,considerable achievements have just been made by the use of structurally unique and reactively rich allenes as coupling partners in recent years.This review summarizes the recent progress of the first-row transition-metal-catalyzed C–H activations with allenes.
基金support from the National Natural Science Foundation of China (Nos.81373259 and 81573286)Sichuan Science and Technology Program (Nos.2020YJ0221 and 2018JY0537)。
文摘Sulfoxonium ylides as carbene precursors couple smoothly with thioureas in the presence of 5 mol% of rhodium(Ⅱ) acetate dimmer via carbenoid insertion to afford the corresponding 2-aminothiazoles with high chemoselectivity,providing a facile and efficient approach to access a variety of 2-aminothiazole derivatives with good functional groups tolerance.
