Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups in...Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.展开更多
A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be ...A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be synthesized in moderate-to-good yields under standard conditions.The versatility of this method is further confirmed by its applicability to large-scale synthesis,product derivatizations,and late-stage functionalization of pharmaceutically relevant molecules.Mechanistic studies reveal that a radical relay mechanism initiated by a single-electron transfer(SET)process is operational.展开更多
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals a...The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes.In contrast,2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals(NCRs) and nucleophiles still remains rarely underexplored.It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes.Herein,we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles(NuH) in high yields and with high regioselectivity.This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required.This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride,ammonia,water,alcohols,and acids which enables the formation of C-N and C-X(X=F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination,diamination and oxoamination of alkenes.展开更多
The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the...The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.展开更多
Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an...Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.展开更多
We report a Ni-catalyzed three-component cross-electrophile coupling of alkynes with alkenyl halides and fluoroalkyl halides to generate fluoroalkyl-incorporated 1,3-dienes.This mild and operationally simple protocol ...We report a Ni-catalyzed three-component cross-electrophile coupling of alkynes with alkenyl halides and fluoroalkyl halides to generate fluoroalkyl-incorporated 1,3-dienes.This mild and operationally simple protocol is distinguished by its broad substrate scope and excellent chemo-,regio-,and stereo-selectivity,offering a new and organometallic agent-free platform for the construction of fluoroalkyl-incorporated diene motifs.Preliminary mechanistic studies have been conducted to probe the potential reaction pathway.展开更多
In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the di...In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives.These 1,n-thiosulfonylation reactions usually feature simple procedures,100%atom economy,and high regioselectivity.This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions,where thiosulfonates act as both a sulfonyl and a sulfenyl component.展开更多
An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reacti...An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.展开更多
This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via ...This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis.These approaches exhibit high regioselectivity,atom econ-omy and broad functionality tolerance.展开更多
A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal-and photosensitizer-free conditions.This newly developed strategy provides strai...A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal-and photosensitizer-free conditions.This newly developed strategy provides straightforward and efficient access to diverse value-added vicinal trifluoromethyl amines without resorting to the pre-functionalized reagents.Mechanistic experiments demonstrate that the approach proceeded through CF_(3)and iminyl two-radicals process,which were generated directly from commercially available benzophenone imine in a novel electron-donor mode via a SET process activated by the bifunctional hypervalent iodine reagents.The synthetic potential of the protocols was further showcased via the condensation/amination sequential cascade,and transformations to accessβ-CF_(3)primary amines.展开更多
A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,...A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.展开更多
1,3‐Dienes are a class of easily accessible and versatile feedstock chemicals that can participate in a wide range of reactions to facilitate the synthesis of various valuable allylic compounds.In the past decades,ra...1,3‐Dienes are a class of easily accessible and versatile feedstock chemicals that can participate in a wide range of reactions to facilitate the synthesis of various valuable allylic compounds.In the past decades,radical methodology has emerged as a powerful tool for organic synthesis by virtue of the fact that diverse highly reactive radical species can usually be generated under mild,neutral and controlled conditions,and allow for rapid generation of molecular complexity.In this review,we critically illustrate the recent advances in the field of radical‐mediated transformations of 1,3‐dienes based on the different radical precursors and working modes.Wherever possible,particular emphasis is also put on the related mechanistic studies and synthetic applications.展开更多
Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization o...Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization of alkenes,catalytic phosphinoylazidation of alkenes has not yet been reported.Here,we describe the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes.The method is practically useful and requires a relatively low loading of catalyst.Mechanistic studies confirmed the radical nature of the reaction and disclosed the unusually low activation energy 4.8 kcal/mol of radical azido group transfer from the azidyl iron(III)phthalocyanine species(PcFeulN3)to a benzylic radical.This work may help to clarify the mechanism of iron-catalyzed azidation,inspire other mechanism studies and spur further synthetic applications.展开更多
Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition ...Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition metal catalysis,the employment of cheap,abundant aryl chlorides as coupling partner is still a challenging task in this field.Herein,we report our first achievement in 1,1-difunctionalization of alkenes with aryl chlorides as coupling partners.The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand.This study provides an efficient protocol for the synthesis of secondary benzyl boronates from easily accessible feedstock chemicals.Furthermore,the distinguished features of this method include excellent 1,1-regio-and chemoselectivity,good functional group tolerance and easily-operational catalytic reaction conditions.展开更多
A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild rea...A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.展开更多
In this study, we outline a versatile method for the preparation of trifluoromethyl-containing unsymmetrical disulfides via catalytic photoredox difunctionalization of alkenes using symmetrical tetrasulfide (RSSSSR) a...In this study, we outline a versatile method for the preparation of trifluoromethyl-containing unsymmetrical disulfides via catalytic photoredox difunctionalization of alkenes using symmetrical tetrasulfide (RSSSSR) and Langlois' reagent (CF_(3)SO_(2)Na). Notably, this method is also suitable for the late-stage modification of pharmaceutical molecule derivatives. Furthermore, a set of experimental investigations, such as radical trapping experiment, scrambling experiment, cyclic voltammetry (CV) measurement, Stern-Volmer analysis, on/off light-control experiments and a radical cascade experiment have been performed to support the photocatalytic reductive quenching cycle and radical-radical coupling reaction pathway.展开更多
Radical-mediated difunctionalization of alkenes has attracted intensive attention from the synthetic community in recent years.Carbon radicals play a pivotal role as reactive intermediates in alkene difunctionalizatio...Radical-mediated difunctionalization of alkenes has attracted intensive attention from the synthetic community in recent years.Carbon radicals play a pivotal role as reactive intermediates in alkene difunctionalization reactions,showcasing remarkable potential in forging both carbon-carbon and carbon-heteroatom bonds.Traditionally,these transformations proceed through the merger of the classical transition metal catalysis,employing metals such as Ag,Ni,Fe,Cu,and among others.Recently,photoredox catalysis has emerged as a powerful tool for enabling challenging molecular transformations and accessing previously inaccessible chemical space in an environmentally benign and mild manner.In the present work,a novel visible-light-induced copper/photoredox dual catalysis for intermolecular multicomponent difunctionalization of alkenes with aqueous sulfoxonium ylides and versatile functional groups has been developed.This reaction system utilizes alkenes and sulfoxonium ylides as easily prepared starting materials,operates under facile and sustainable conditions,and does not require the addition of acids or bases.Furthermore,the scalable protocol allows for the incorporation of a wide array of alkenes,sulfoxonium ylides,and external protic nucleophiles,including water,chloride,bromide,azide,and thiol.The general system provides a viable access to structurally C(sp^(3))-richγ-hydroxylketones,organic halides,organic sulfides,and azide compounds with excellent chemo-and regioselectivity.Mechanistic investigations imply that two distinct reaction pathways are involved in the generation of carbon radicals from sulfoxonium ylides through a mild visible-light-driven proton-coupled electron transfer(PCET)strategy in the absence or presence of copper salts.This dual catalytic system will establish a novel paradigm,thereby expanding the scope of carbon radical-mediated transformations of olefins.展开更多
Herein, it is reported that a palladium/bidentate amine ligand cooperative catalytic system has been developed to achieve the intramolecular cyclization of 1,6-enyne coupled with a Suzuki cross-coupling reaction, succ...Herein, it is reported that a palladium/bidentate amine ligand cooperative catalytic system has been developed to achieve the intramolecular cyclization of 1,6-enyne coupled with a Suzuki cross-coupling reaction, successfully constructing a diaryl-substituted γ-butyrolactam skeleton. The tandem catalytic mechanism significantly enhances synthetic efficiency by circumventing the isolation and purification of intermediates required in traditional stepwise synthesis, demonstrating exceptional step economy. This method provides a novel modular strategy for the rapid assembly of bioactive diaryl-containing lactam compound libraries.展开更多
An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which...An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which provides a useful strategy for the rapid synthesis of sulfur-containing imides with broad substrate scope and high functional tolerance.It is a rare example of in situ generation of O-acyl isoamide precursor for Mumm rearrangement.展开更多
The selective radical hydroalkylation of 1,3-dienes,particularly using readily available alkyl radical sources,remains a challenging synthetic transformation,primarily due to the high reactivity of radical intermediat...The selective radical hydroalkylation of 1,3-dienes,particularly using readily available alkyl radical sources,remains a challenging synthetic transformation,primarily due to the high reactivity of radical intermediates and the presence of multiple reactive sites within the 1,3-diene framework.Herein,we disclose a mild and efficient visible-light-driven 1,4-hydroalkylation of conjugated dienes with perfect atom economy.展开更多
文摘Difunctionalization of unsaturated hydrocarbons is a pivotal synthetic strategy enabling the conversion of alkenes and alkynes into high value-added compounds.It allows for the introduction of two functional groups into the unsaturated bond in a single step,facilitating the efficient construction of complex molecular architectures,which has been widely utilized in material chemistry,pharmaceutical and fine chemical synthesis.Recently,significant progress has been made via free radical-mediated difunctionalization due to the extensive application of photocatalysis.However,highly selective difunc-tionalization reactions still remain challenging.The research progress of selective difunctionalization of unsaturated hydro-carbons using a free radical addition/functional group migration strategy over the past decade is summarized,and synthetic strategies and key reaction steps are systematically elaborated.
基金Project supported by the Natural Science Foundation of Zhejiang Province(No.LMS25B060007)。
文摘A practical method for the 1,3-azidoheteroarylation of[1.1.1]propellane with cyclic aldimines and azidotrimethylsilane(TMSN_(3))is presented.A broad spectrum of 1-azido-3-heteroaryl bicyclo[1.1.1]pentanes(BCPs)can be synthesized in moderate-to-good yields under standard conditions.The versatility of this method is further confirmed by its applicability to large-scale synthesis,product derivatizations,and late-stage functionalization of pharmaceutically relevant molecules.Mechanistic studies reveal that a radical relay mechanism initiated by a single-electron transfer(SET)process is operational.
基金the National Science Foundation of China(No.22071058)the Fundamental Research Funds for the Central Universities for financial support。
文摘The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds.The existing approach is extensively promoted by using C/Xcentered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes.In contrast,2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals(NCRs) and nucleophiles still remains rarely underexplored.It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes.Herein,we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles(NuH) in high yields and with high regioselectivity.This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required.This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride,ammonia,water,alcohols,and acids which enables the formation of C-N and C-X(X=F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination,diamination and oxoamination of alkenes.
基金the National Natural Science Foundation of China(No.21901199)National Training Program of Innovation and Entrepreneurship for Undergraduates(No.S202310698011)Xi’an Jiaotong University(No.7121192002)for financial support.
文摘The radical difunctionalization of alkenes with sulfonyl bifunctional represents a powerful and straightforward approach to access functionalized alkane derivatives.However,both the mechanistic activation mode and the substrate scopes of this type of radical difunctionalizations are still limited.We demonstrate herein a modular photoredox strategy for the difunctionalization of alkenes,employing arylsulfonyl acetate as the bifunctional reagent.This approach involves a radical addition/Smiles rearrangement cascade process,offering a robust alternative for the synthesis of valuableγ,γ-diaryl andγ-aryl esters.A complementary oxidative bifunctional reagents activation mode is identified to govern the radical cascade reactions,facilitating the simultaneous incorporation of aryl and carboxylate-bearing alkyl groups into the alkenes with excellent diastereoselectivity.Noteworthy features of this method include mild reaction conditions,organophotocatalysis,high atom-and step-economy,excellent functional group compatibility and great structural diversity.
基金supported by Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the National Natural Science Foundation of China(21472162,21772171)the National Basic Research Program of China(2015CB856600)~~
文摘Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.
基金financial support provided by the National Natural Science Foundation of China(Nos.21991123,21971036,21901036)the Shanghai Rising-Star Program(No.20QA1400200)。
文摘We report a Ni-catalyzed three-component cross-electrophile coupling of alkynes with alkenyl halides and fluoroalkyl halides to generate fluoroalkyl-incorporated 1,3-dienes.This mild and operationally simple protocol is distinguished by its broad substrate scope and excellent chemo-,regio-,and stereo-selectivity,offering a new and organometallic agent-free platform for the construction of fluoroalkyl-incorporated diene motifs.Preliminary mechanistic studies have been conducted to probe the potential reaction pathway.
基金financial support from the Natural Science Foundation of China(No.22001121)Natural Science Foundation of Jiangsu Province(No.BK20180690)+1 种基金Nanjing Tech University(Start-up Grant Nos.39837118 and39837146)Xuzhou Medical University(Start-up Grant No.RC20552038)。
文摘In recent years,the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives.These 1,n-thiosulfonylation reactions usually feature simple procedures,100%atom economy,and high regioselectivity.This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions,where thiosulfonates act as both a sulfonyl and a sulfenyl component.
基金Financial support was provided by Hong Kong RGC (No. 16302318)Shenzhen Science and Technology Innovation Committee (No. JCYJ20170818113708560)HKUST (No. IEG17SC03)
文摘An electrochemical vicinal heterodifunctionalization of olefins for the synthesis ofβ-oxysulfones is described.With suitable choice of the conditions,including current,electrodes,and electrolyte,this oxidation reaction proceeded efficiently in an undivided cell without the use of a stoichiometric chemical oxidant.In addition to the previously established synthesis ofβ-hydroxysulfones in the presence of water,minor modification of this protocol by using either external alcohol nucleophiles or internal carboxylic acid nucleophile also led to the synthesis ofβ-alkoxysulfones,andβ-sulfonyl lactones.
基金support from the National Natural Science Foundation of China(Nos.21971107,22071101,22271147).
文摘This work describes intermolecular acylfluorination of gem-difluoroenynes using acyl fluorides as both acyl source and fluorine source.Trifluoromethyl-substituted allenones or furans could be selectively achieved via phosphine and silver catalysis.These approaches exhibit high regioselectivity,atom econ-omy and broad functionality tolerance.
基金Financial support from the National Natural Science Foundation of China(Nos.22201239,22205192 and 22271244)the Hunan Provincial Natural Science Foundation of China(No.2022JJ40429)+2 种基金the Scientific Research Fund of Hunan Provincial Education Department(No.21B0130)the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(No.2022C02)the Process Intensification&Green Chemical Engineering Innovation Team Project of Hunan Province。
文摘A highly site-selective intermolecular trifluoromethylimination of activated and unactivated olefins was reported under transition-metal-and photosensitizer-free conditions.This newly developed strategy provides straightforward and efficient access to diverse value-added vicinal trifluoromethyl amines without resorting to the pre-functionalized reagents.Mechanistic experiments demonstrate that the approach proceeded through CF_(3)and iminyl two-radicals process,which were generated directly from commercially available benzophenone imine in a novel electron-donor mode via a SET process activated by the bifunctional hypervalent iodine reagents.The synthetic potential of the protocols was further showcased via the condensation/amination sequential cascade,and transformations to accessβ-CF_(3)primary amines.
基金financial support from the National Natural Science Foundation of China(No.22171215)the Excellent Youth Foundation of Hubei Scientific Committee(No.2022CFA092)the GuangDong Basic and Applied Basic Research Foundation(No.2022A1515110113).
文摘A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes,B_(2)Pin_(2) and alkene-tethered aryl halides is reported.This reaction proceeds under mild conditions and shows broad sub-strate scope,providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity.This transformation fea-tures the catalytic generation ofβ-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings.An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenyl-boronate moiety.
文摘1,3‐Dienes are a class of easily accessible and versatile feedstock chemicals that can participate in a wide range of reactions to facilitate the synthesis of various valuable allylic compounds.In the past decades,radical methodology has emerged as a powerful tool for organic synthesis by virtue of the fact that diverse highly reactive radical species can usually be generated under mild,neutral and controlled conditions,and allow for rapid generation of molecular complexity.In this review,we critically illustrate the recent advances in the field of radical‐mediated transformations of 1,3‐dienes based on the different radical precursors and working modes.Wherever possible,particular emphasis is also put on the related mechanistic studies and synthetic applications.
文摘Phosphinoylazidation of alkenes is a direct method to build nitrogen-and phosphorus-containing compounds from feed-stock chemicals.Notwithstanding the advances in other phosphinyl radical related difunctionalization of alkenes,catalytic phosphinoylazidation of alkenes has not yet been reported.Here,we describe the first iron-catalyzed intermolecular phosphinoylazidation of styrenes and unactivated alkenes.The method is practically useful and requires a relatively low loading of catalyst.Mechanistic studies confirmed the radical nature of the reaction and disclosed the unusually low activation energy 4.8 kcal/mol of radical azido group transfer from the azidyl iron(III)phthalocyanine species(PcFeulN3)to a benzylic radical.This work may help to clarify the mechanism of iron-catalyzed azidation,inspire other mechanism studies and spur further synthetic applications.
基金supported by grants from the National Natural Science Foundation of China(No.22122107)the Fundamental Research Funds for Central Universities(No.2042021kf0190).
文摘Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition metal catalysis,the employment of cheap,abundant aryl chlorides as coupling partner is still a challenging task in this field.Herein,we report our first achievement in 1,1-difunctionalization of alkenes with aryl chlorides as coupling partners.The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand.This study provides an efficient protocol for the synthesis of secondary benzyl boronates from easily accessible feedstock chemicals.Furthermore,the distinguished features of this method include excellent 1,1-regio-and chemoselectivity,good functional group tolerance and easily-operational catalytic reaction conditions.
文摘A photoredox-catalyzed cascade carbon/carboxylation of activated alkenes with malonates acetals and CO_(2) has been achieved,leading to a range of functionalized 1,1,3-tricarboxylates in good efficiency under mild reaction conditions.This reaction provides a facile and sustainable method for the synthesis of tricarboxylates by using CO_(2) as the carboxylic source.
基金supported by the Special Projects in Key Fields of Colleges and Universities in Guangdong Province(2024ZDZX2078)the Basic and Applied Basic Research Fund Project of Guangdong Province(2023A1515110852)Special Funds of Key Disciplines Construction from Guangdong and Zhongshan Cooperating.
文摘In this study, we outline a versatile method for the preparation of trifluoromethyl-containing unsymmetrical disulfides via catalytic photoredox difunctionalization of alkenes using symmetrical tetrasulfide (RSSSSR) and Langlois' reagent (CF_(3)SO_(2)Na). Notably, this method is also suitable for the late-stage modification of pharmaceutical molecule derivatives. Furthermore, a set of experimental investigations, such as radical trapping experiment, scrambling experiment, cyclic voltammetry (CV) measurement, Stern-Volmer analysis, on/off light-control experiments and a radical cascade experiment have been performed to support the photocatalytic reductive quenching cycle and radical-radical coupling reaction pathway.
基金supported by the National Natural Science Foundation of China(22071211)the Hunan Provincial Innovation Foundation for Postgraduate(XDCX2024Y215)the Open Research Fund of School of Chemistry and Chemical Engineering of Henan Normal University(2022C02).
文摘Radical-mediated difunctionalization of alkenes has attracted intensive attention from the synthetic community in recent years.Carbon radicals play a pivotal role as reactive intermediates in alkene difunctionalization reactions,showcasing remarkable potential in forging both carbon-carbon and carbon-heteroatom bonds.Traditionally,these transformations proceed through the merger of the classical transition metal catalysis,employing metals such as Ag,Ni,Fe,Cu,and among others.Recently,photoredox catalysis has emerged as a powerful tool for enabling challenging molecular transformations and accessing previously inaccessible chemical space in an environmentally benign and mild manner.In the present work,a novel visible-light-induced copper/photoredox dual catalysis for intermolecular multicomponent difunctionalization of alkenes with aqueous sulfoxonium ylides and versatile functional groups has been developed.This reaction system utilizes alkenes and sulfoxonium ylides as easily prepared starting materials,operates under facile and sustainable conditions,and does not require the addition of acids or bases.Furthermore,the scalable protocol allows for the incorporation of a wide array of alkenes,sulfoxonium ylides,and external protic nucleophiles,including water,chloride,bromide,azide,and thiol.The general system provides a viable access to structurally C(sp^(3))-richγ-hydroxylketones,organic halides,organic sulfides,and azide compounds with excellent chemo-and regioselectivity.Mechanistic investigations imply that two distinct reaction pathways are involved in the generation of carbon radicals from sulfoxonium ylides through a mild visible-light-driven proton-coupled electron transfer(PCET)strategy in the absence or presence of copper salts.This dual catalytic system will establish a novel paradigm,thereby expanding the scope of carbon radical-mediated transformations of olefins.
基金the National Key Research and Development Program of China(2022YFB4101800)the National Natural Science Foundation of China(22231002)the Guangdong Basic and Applied Basic Research Foundation(2024B1515040027)for their financial support.
文摘Herein, it is reported that a palladium/bidentate amine ligand cooperative catalytic system has been developed to achieve the intramolecular cyclization of 1,6-enyne coupled with a Suzuki cross-coupling reaction, successfully constructing a diaryl-substituted γ-butyrolactam skeleton. The tandem catalytic mechanism significantly enhances synthetic efficiency by circumventing the isolation and purification of intermediates required in traditional stepwise synthesis, demonstrating exceptional step economy. This method provides a novel modular strategy for the rapid assembly of bioactive diaryl-containing lactam compound libraries.
基金support from the Science and Technology Innovation Program of Hunan Province(No.2021RC2079)China Postdoctoral Science Foundation(Nos.2022T150075 and 2022M720541)+2 种基金Hunan Provincial Department of Education Outstanding Youth Project(No.22B0212)Tianjin Synthetic Biotechnology Innovation Capacity Improvement Project(No.TSBI-CIP-CXRC-038)National College Students Innovation and Entrepreneurship Training Program(No.S202210537024).
文摘An efficient and practical electrochemical method for the three-component reaction cascade Mumm rearrangement of imides has been developed using a simple undivided cell with carbon electrodes at room temperature,which provides a useful strategy for the rapid synthesis of sulfur-containing imides with broad substrate scope and high functional tolerance.It is a rare example of in situ generation of O-acyl isoamide precursor for Mumm rearrangement.
基金National Natural Science Foundation of China(No.22301109)the Research Funds for Talent Introduction of Jiangsu Ocean University(No.KQ23065)+1 种基金Lianyungang Haiyan project(No.KK24005)Postgraduate Research&Practice Innovation Program of Jiangsu Province(SJCX24_2095).
文摘The selective radical hydroalkylation of 1,3-dienes,particularly using readily available alkyl radical sources,remains a challenging synthetic transformation,primarily due to the high reactivity of radical intermediates and the presence of multiple reactive sites within the 1,3-diene framework.Herein,we disclose a mild and efficient visible-light-driven 1,4-hydroalkylation of conjugated dienes with perfect atom economy.
