Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylatio...Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.展开更多
We report a hydrogen-evolution dimerization of styrenes via the synergistic merger of Acr＋-Mes photocatalyst and cobaloxime proton reduction catalysts. By utilizing this dual catalyst system, 1,2-dihydro-1-arylnaphth...We report a hydrogen-evolution dimerization of styrenes via the synergistic merger of Acr＋-Mes photocatalyst and cobaloxime proton reduction catalysts. By utilizing this dual catalyst system, 1,2-dihydro-1-arylnaphthalene derivatives can be directly constructed from commercially available styrenes. Our reaction proceeds smoothly under mild conditions without the need for oxidants or hydrogen atom transfer reagents, and the sole byproduct is hydrogen gas. Mechanistic investigation suggests that the reaction is initiated by photoinduced electron transfer under visible-light irradiation.展开更多
α-(Trifluoromethyl)styrene and its derivatives have found wide applications in the fields of pharmaceuti-cals,agrochemicals,and advanced materials.They are also versatile trifluoromethyl-containing building blocks fo...α-(Trifluoromethyl)styrene and its derivatives have found wide applications in the fields of pharmaceuti-cals,agrochemicals,and advanced materials.They are also versatile trifluoromethyl-containing building blocks for the preparation of various trifluoromethyl-containing,fluorine-containing or nonfluorinated compounds.Recently,great efforts have been made to develop diverse reactions for rapidly accessing a wide range of valuable gem–difluoroalkenes and gem–difluoroalkylated compounds via defluorinative re-action or the defluorinative ipso-functionalization reaction ofα-(trifluoromethyl)styrenes,respectively.In contrast,α-(trifluoromethyl)styrenes remain notably underdeveloped with respect to their use in cycload-dition and hydroaddition reaction with retaining of three C–F bonds.This short review herein is aimed to summarize the recent progress on the cycloaddition and hydroaddition reaction including nucleophilic,radical and transition metal-catalyzed addition ofα-(trifluoromethyl)styrenes without accompanying de-fluorination.展开更多
Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alk...Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.展开更多
Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free co...Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.展开更多
Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate ...Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate the physical,chemical,and biological properties of organic molecules–into aminosilylalkane remains a challenge.Herein,we report a cobalt-catalyzed silyldifluoromethylamination of styrenes using TMSCF_(2)H and nitrogen nucleophiles.By employing readily available starting materials,a series of complex,highly functionalized aminosilyldifluoroalkane derivatives were synthesized in moderate to good yields.This methodology establishes a novel strategy for constructing organosilicon compounds,complementing existing synthetic approaches.展开更多
A photochemically induced carbon monoxide-inclusive four-component carbonylation reaction has been delineated,facilitating the diacylation of styrenes with acyl azolium salts to synthesize valuable 1,4-diketone compou...A photochemically induced carbon monoxide-inclusive four-component carbonylation reaction has been delineated,facilitating the diacylation of styrenes with acyl azolium salts to synthesize valuable 1,4-diketone compounds with moderate to good yields.This process proceeds by generating acyl radicals from the Hantzsch esters and carbon monoxide,which subsequently add to the terminal position of styrenes.Then,under light irradiation,the newly generated carbon radical can further react with activated acyl azolium salts to finish the desired 1,4-diketone products.展开更多
A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and...A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and these groups have been further converted to high-value functional groups.Detailed mechanistic experiments have proven that the single-electron reduction of CO_(2) is the key to this unique regioselectivity.展开更多
γ-Hydroxy acid has widespread applications in materials,pharmaceuticals,food industries and organic synthesis.In this context,the CO_(2)-involved multi-component reaction of the C-C unsaturated bond represents one of...γ-Hydroxy acid has widespread applications in materials,pharmaceuticals,food industries and organic synthesis.In this context,the CO_(2)-involved multi-component reaction of the C-C unsaturated bond represents one of the most promising strategies for preparingγ-hydroxy acids from readily available feedstocks in one step.However,current reports mainly rely on the utilization of limited-access reagents and even stoichiometric metal catalysts,which suppress their application.Herein,we describe a novel example of γ-hydroxy acids enabled by photocatalyzed carboxylative alkylation of styrenes with easy-access aliphatic aldehydes and CO_(2).This protocol offers a facile tool to furnish a variety of γ-hydroxy acids with good functional group compatibility and can be further applied to the late-stage modification of biomolecules,as well as ligation of drug fragments.The developed reaction can be seamlessly scaled up using flow technology,rendering its practicality.Additionally,this platform enables the downstream synthesis of furan-2(5H)-one 67,which shows attractive anti-cancer efficacy against a set of tumor cells,further highlighting the significance of our protocol.展开更多
An efficient and broadly applicable protocol for the aerobic coupling of styrenes with sulfonylhydrazides has been developed that affords P-ketosulfones bearing various functional groups in moderate to excellent yield...An efficient and broadly applicable protocol for the aerobic coupling of styrenes with sulfonylhydrazides has been developed that affords P-ketosulfones bearing various functional groups in moderate to excellent yields.The preliminary experimental results support the involvement of active benzyl radical species,and a radical pathway was therefore proposed for the reaction.展开更多
We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically ...We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically usefulβ-boryl quaternary aldehydes and cyclopropyl boronate esters bearing a quaternary carbon center.With NHC(IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)as the ligand,the carbene intermediate reacts with O-H bond of alcohol while the carbene intermediate would undergo C-H bond insertion when using phosphine ligand[1,2-bis(diphenylphospino)ethane]as the ligand.Formation of a carbene intermediate has been proposed as the key step for this transformation.展开更多
The fluorescence quenching coefficient (Ksv) and the quenching rate constant kq of ten para-substituted styrenes (1-Ys) have been measured and correlation-analyzed by both the dual-parameter equation (Eq. 1) with (ρx...The fluorescence quenching coefficient (Ksv) and the quenching rate constant kq of ten para-substituted styrenes (1-Ys) have been measured and correlation-analyzed by both the dual-parameter equation (Eq. 1) with (ρxσx+ρ'σ') and the single-parameter equation (Eq. 2) with ρxσx. Ex-cellent results have been obtained for the correlation of KSV against (ρxσmb+ρ'σ'JJ) or (ρxσ+ +ρ'σ'JJ). Our results suggest that, possibly, there might be no need to use excited-state substituent constant for the fluorecence quenching process of excited states of styrenes.展开更多
A novel and practical method for the synthesis of 3,5-bis(trifluoromethyl)-4,5-dihydro-1H-pyrazoles by [3+2] cycloaddition reactions of α-(trifluoromethyl)styrenes with 2,2,2-trifluorodiazoethane (CF3CHN2) has been d...A novel and practical method for the synthesis of 3,5-bis(trifluoromethyl)-4,5-dihydro-1H-pyrazoles by [3+2] cycloaddition reactions of α-(trifluoromethyl)styrenes with 2,2,2-trifluorodiazoethane (CF3CHN2) has been developed. The cyclization reaction proceeds smoothly in the presence of a catalytic amount of Et_(3)N, affording a variety of bis(trifluoromethyl)-substituted 2-pyrazolines in good to excellent yields. This method also exhibits a broad substrate scope and tolerates various functional groups.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
A[4+2]annulation of two different styrenes to construct polysubstituted 1,2-dihydronaphthalenes was achieved.This transformation proceeded smoothly under electrochemical oxidative conditions without metal catalysts an...A[4+2]annulation of two different styrenes to construct polysubstituted 1,2-dihydronaphthalenes was achieved.This transformation proceeded smoothly under electrochemical oxidative conditions without metal catalysts and external oxidants.A series of polysubstituted 1,2-dihydronaphthalenes were obtained with high regioselectivity and diastereoselectivity.Moreover,polysubstituted 1,2-dihydronaphthalenes were further transformed to polysubstituted 1,2,3,4-tetrahydronaphthalenes and polysubstituted naphthalenes,which show great potential in synthetic applications.展开更多
The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl...The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).展开更多
Transition metal-catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond.Recently,the incorporation of organometallic reag...Transition metal-catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond.Recently,the incorporation of organometallic reagent with the CO gas as a nucleophilic acyl synthon could enable the acylmetallation reaction,which greatly increases the horizon of carbometallation chemistry.Herein,we report a nickel-catalyzed regiodivergent acylzincation of o-cyano cinnamate ester and o-cyano styrene,in which the cyano moiety intramolecularly captures zinc intermediates to trigger the tandem cyclization process.This protocol features mild conditions,broad substrate scope and excellent functional group tolerance,thus affording a diverse array of highly functionalized carbocyclic compounds.展开更多
As a readily available feedstock,styrene with about 25 million tons of global annual production serves as an important building block and organic synthon for the synthesis of fine chemicals,polystyrene plastics,and el...As a readily available feedstock,styrene with about 25 million tons of global annual production serves as an important building block and organic synthon for the synthesis of fine chemicals,polystyrene plastics,and elastomers.Thus,in the past decades,many direct transformations of this costless styrene feedstock were disclosed for the preparation of high-value chemicals,which to date,generally performed on the functionalization of styrenes through the allylic C-H bond,C(sp2)-H bond,or the C=C double bond cleavage.However,the dealkenylative functionalization of styrenes via the direct C-C single bond cleavage is so far challenging and still unknown.Herein,we report the novel and efficient C-C amination and hydroxylation reactions of styrenes for the synthesis of valuable aryl amines and phenols via the site-selective C(Ar)-C(alkenyl)single bond cleavage.This chemistry unlocks the new transformation and application of the styrene feedstock and provides an efficient protocol for the late-stage modification of substituted styrenes with the site-directed dealkenylative amination and hydroxylation.展开更多
Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difu...Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difunctionalization reaction could undergo smoothly using 1 mol%catalyst loading with good functional group tolerance.Not only di-and tri-substituted hydrosilanes,but also alkoxysilane is suitable,which does explore the scope of the family of 1-amino-2-silyl compounds.The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot,two-step transformations.The primary mechanism has been proposed based on the control experiments.展开更多
Summary of main observation and conclusion Herein,unprecedented rhenium-catalyzed decarboxylative oxytri-/difluoromethylation and Heck-type trifluoromethylation of styrenes have been developed by using hypervalent iod...Summary of main observation and conclusion Herein,unprecedented rhenium-catalyzed decarboxylative oxytri-/difluoromethylation and Heck-type trifluoromethylation of styrenes have been developed by using hypervalent iodine(Ⅲ)reagents derived from cheap,stable,and easy-handling fluorinated carboxylic acids.Mechanistic studies revealed a radical decarboxylative trifluoromethylation pathway occurring in these reactions.展开更多
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Chiral 3-aryl alkanoic acids and their derivatives present a class of highly valued framework in natural products and pharmaceuticals.Among multifarious synthetic strategies,asymmetric intermolecular hydrocarbonylation ofα-alkyl styrenes exhibit high atom-economy and straightforwardness,nonetheless facing problems in simultaneously addressing the activity,chemoselectivity,regioselectivity and stereoselectivity of the strategy,which remain unresolved to date.Herein,we disclosed an enantioselective Pd-catalyzed exclusive anti-Markovnikov hydroesterification ofα-alkyl styrenes with thiols(hydrothiocarbonylation).The catalytic system,consisting of Pd source,chiral sulfoxide phosphine ligand(SOP),pTs OH·H_(2)O and Li Cl,efficiently achieved the correspondingα-chiral 3-aryl alkanoic thioesters in excellent results(68 examples,up to 99%yield,generally 90%-98%ee).The chloride anion from lithium chloride(Li Cl)acts as a coordinating ligand for palladium,promoting the activity while simultaneously enhancing stereochemical control.Moreover,the potential of the method was demonstrated by the late-stage functionalization of natural products,formal synthesis of biologically active molecules intermediates(RC-33,AM-6226)as well as intermediate analogue of R-106578.
基金supported by the Ministry of Science and Technology of China (2014CB239402, 2017YFA0206903)the National Natural Science foundation of China (21390404)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Science (XDB17000000)the Key Research Pro-gram of Frontier Sciences, the Chinese Academy of Sciences (QYZDY-SSW-JSC029)~~
文摘We report a hydrogen-evolution dimerization of styrenes via the synergistic merger of Acr＋-Mes photocatalyst and cobaloxime proton reduction catalysts. By utilizing this dual catalyst system, 1,2-dihydro-1-arylnaphthalene derivatives can be directly constructed from commercially available styrenes. Our reaction proceeds smoothly under mild conditions without the need for oxidants or hydrogen atom transfer reagents, and the sole byproduct is hydrogen gas. Mechanistic investigation suggests that the reaction is initiated by photoinduced electron transfer under visible-light irradiation.
基金support from the National Natural Science Foundation of China (No. 21472043)
文摘α-(Trifluoromethyl)styrene and its derivatives have found wide applications in the fields of pharmaceuti-cals,agrochemicals,and advanced materials.They are also versatile trifluoromethyl-containing building blocks for the preparation of various trifluoromethyl-containing,fluorine-containing or nonfluorinated compounds.Recently,great efforts have been made to develop diverse reactions for rapidly accessing a wide range of valuable gem–difluoroalkenes and gem–difluoroalkylated compounds via defluorinative re-action or the defluorinative ipso-functionalization reaction ofα-(trifluoromethyl)styrenes,respectively.In contrast,α-(trifluoromethyl)styrenes remain notably underdeveloped with respect to their use in cycload-dition and hydroaddition reaction with retaining of three C–F bonds.This short review herein is aimed to summarize the recent progress on the cycloaddition and hydroaddition reaction including nucleophilic,radical and transition metal-catalyzed addition ofα-(trifluoromethyl)styrenes without accompanying de-fluorination.
基金This work was supported by grants from the National Natural Science Foundation of China(No.22122107)the Fundamental Research Funds for Central Universities(No.2042021kf0190).
文摘Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.
文摘Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.
基金supported by Fundamental Research Program of Shanxi Province(No.202303021211006)Shanxi Scholarship Council of China(No.2023-032).
文摘Aminosilylalkanes are important motifs in bioactive molecules,yet methods for their direct incorporation remain limited.In particular,the efficient introduction of gem-difluoro groups–known to significantly modulate the physical,chemical,and biological properties of organic molecules–into aminosilylalkane remains a challenge.Herein,we report a cobalt-catalyzed silyldifluoromethylamination of styrenes using TMSCF_(2)H and nitrogen nucleophiles.By employing readily available starting materials,a series of complex,highly functionalized aminosilyldifluoroalkane derivatives were synthesized in moderate to good yields.This methodology establishes a novel strategy for constructing organosilicon compounds,complementing existing synthetic approaches.
基金supported by the National Key R&D Program of China(2023YFA1507500)the Chinese Scholarship Council。
文摘A photochemically induced carbon monoxide-inclusive four-component carbonylation reaction has been delineated,facilitating the diacylation of styrenes with acyl azolium salts to synthesize valuable 1,4-diketone compounds with moderate to good yields.This process proceeds by generating acyl radicals from the Hantzsch esters and carbon monoxide,which subsequently add to the terminal position of styrenes.Then,under light irradiation,the newly generated carbon radical can further react with activated acyl azolium salts to finish the desired 1,4-diketone products.
基金supported by the National Key R&D Program of China(2023YFA1507203)the National Natural Science Foundation of China(22371149,22301144,and 22188101)+3 种基金the Natural Science Foundation of Tianjin(24JCJQJC00210)the Fundamental Research Funds for the Central Universities(63223015)Frontiers Science Center for New Organic Matter,Nankai University(63181206)Nankai University are gratefully acknowledged.
文摘A general strategy forβ-selective silylcarbonylation of styrenes with CO_(2) via electrochemical reduction has been reported.A series of styrenes have been simultaneously introduced with silyl and carboxyl groups,and these groups have been further converted to high-value functional groups.Detailed mechanistic experiments have proven that the single-electron reduction of CO_(2) is the key to this unique regioselectivity.
基金supported by the“Thousand Talents Plan”Youth Programthe National Natural Science Foundations of China(22101136,22478200)+1 种基金the Fundamental Research Funds for the Central Universities(DUT23LAB612,DUT25RC(3)049)the Foundation of Guizhou Educational Committee(qianjiaoji[2023]088)。
文摘γ-Hydroxy acid has widespread applications in materials,pharmaceuticals,food industries and organic synthesis.In this context,the CO_(2)-involved multi-component reaction of the C-C unsaturated bond represents one of the most promising strategies for preparingγ-hydroxy acids from readily available feedstocks in one step.However,current reports mainly rely on the utilization of limited-access reagents and even stoichiometric metal catalysts,which suppress their application.Herein,we describe a novel example of γ-hydroxy acids enabled by photocatalyzed carboxylative alkylation of styrenes with easy-access aliphatic aldehydes and CO_(2).This protocol offers a facile tool to furnish a variety of γ-hydroxy acids with good functional group compatibility and can be further applied to the late-stage modification of biomolecules,as well as ligation of drug fragments.The developed reaction can be seamlessly scaled up using flow technology,rendering its practicality.Additionally,this platform enables the downstream synthesis of furan-2(5H)-one 67,which shows attractive anti-cancer efficacy against a set of tumor cells,further highlighting the significance of our protocol.
基金supported by the National Natural Science Foundation of China(U1504210)the China Postdoctoral Science Foundation funded project(2015M572110)Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis(130028651)
文摘An efficient and broadly applicable protocol for the aerobic coupling of styrenes with sulfonylhydrazides has been developed that affords P-ketosulfones bearing various functional groups in moderate to excellent yields.The preliminary experimental results support the involvement of active benzyl radical species,and a radical pathway was therefore proposed for the reaction.
基金appreciate the financial support from DICP(Dalian Institute of Chemical Physics,CAS)and the K.C.Wong Education Foundation(grant no.GJTD-2020-08).
文摘We report a copper-catalyzed ligand-controlled selective carbonylative borofunctionalization ofα-substituted styrenes.This reaction provides a general and versatile procedure to synthesize a variety of synthetically usefulβ-boryl quaternary aldehydes and cyclopropyl boronate esters bearing a quaternary carbon center.With NHC(IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene)as the ligand,the carbene intermediate reacts with O-H bond of alcohol while the carbene intermediate would undergo C-H bond insertion when using phosphine ligand[1,2-bis(diphenylphospino)ethane]as the ligand.Formation of a carbene intermediate has been proposed as the key step for this transformation.
基金Project supported by the National Natural Science Foundation of China
文摘The fluorescence quenching coefficient (Ksv) and the quenching rate constant kq of ten para-substituted styrenes (1-Ys) have been measured and correlation-analyzed by both the dual-parameter equation (Eq. 1) with (ρxσx+ρ'σ') and the single-parameter equation (Eq. 2) with ρxσx. Ex-cellent results have been obtained for the correlation of KSV against (ρxσmb+ρ'σ'JJ) or (ρxσ+ +ρ'σ'JJ). Our results suggest that, possibly, there might be no need to use excited-state substituent constant for the fluorecence quenching process of excited states of styrenes.
基金support from the National Key Research and Development Program of China(No.2017YFD0200505)。
文摘A novel and practical method for the synthesis of 3,5-bis(trifluoromethyl)-4,5-dihydro-1H-pyrazoles by [3+2] cycloaddition reactions of α-(trifluoromethyl)styrenes with 2,2,2-trifluorodiazoethane (CF3CHN2) has been developed. The cyclization reaction proceeds smoothly in the presence of a catalytic amount of Et_(3)N, affording a variety of bis(trifluoromethyl)-substituted 2-pyrazolines in good to excellent yields. This method also exhibits a broad substrate scope and tolerates various functional groups.
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supported by the National Natural Science Foundation of China(22031008)Science Foundation of Wuhan(2020010601012192)The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated.
文摘A[4+2]annulation of two different styrenes to construct polysubstituted 1,2-dihydronaphthalenes was achieved.This transformation proceeded smoothly under electrochemical oxidative conditions without metal catalysts and external oxidants.A series of polysubstituted 1,2-dihydronaphthalenes were obtained with high regioselectivity and diastereoselectivity.Moreover,polysubstituted 1,2-dihydronaphthalenes were further transformed to polysubstituted 1,2,3,4-tetrahydronaphthalenes and polysubstituted naphthalenes,which show great potential in synthetic applications.
基金We are grateful for financial support from the National Nature Science Foundation of China(Nos.21532009,91956202,21821002 and 21790330)the Science and Technology Commission of Shanghai Municipality(Nos.20JC1417000,19590750400 and 17JC1401200)+2 种基金the strategic Priority Research Program(No.XDB20000000)the Key Research Program of Frontier Science(QYZDJSSWSLH055)the International Partnership Program(No.121731KY5B20190016)of the Chinese Academy of Sciences.
文摘The first copper-catalyzed enantioselective arylcyanation of styrenes has been developed using readily available anilines as aryl radical precursors under mild conditions,which enables easy access to chiral 2,3-diaryl propionitriles with moderate to good enantiose-lectivities.This operationally straightforward reaction exhibits broad substrate scope and functional group tolerance.Notably,this method has been applied to the synthesis of chiral AlEgen as well as estrogen receptor-B agonist(R)-diarylpropionitrile(DPN).
基金supported by the National Natural Science Foundation of China(22171079,22371071)the Natural Science Foundation of Shanghai(21ZR1480400)+5 种基金the Shanghai Rising-Star Program(20QA1402300)the Shanghai Sailing Program(23YF1408800)the Shanghai Municipal Science and Technology Major Project(Grant No.2018SHZDZX03)the Program of Introducing Talents of Discipline to Universities(B16017)the China Postdoctoral Science Foundation(2021M701197,2023T160215)the Fundamental Research Funds for the Central Universities.
文摘Transition metal-catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond.Recently,the incorporation of organometallic reagent with the CO gas as a nucleophilic acyl synthon could enable the acylmetallation reaction,which greatly increases the horizon of carbometallation chemistry.Herein,we report a nickel-catalyzed regiodivergent acylzincation of o-cyano cinnamate ester and o-cyano styrene,in which the cyano moiety intramolecularly captures zinc intermediates to trigger the tandem cyclization process.This protocol features mild conditions,broad substrate scope and excellent functional group tolerance,thus affording a diverse array of highly functionalized carbocyclic compounds.
基金This study was financially supported from the National Natural Science Foundation of China(Nos.21632001,21772002,81821004)the Drug Innovation Major Project(2018ZX09711-001)+1 种基金Peking University Health Science Center(No.BMU20160541)the Open Research Fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes which are greatly appreciated.
文摘As a readily available feedstock,styrene with about 25 million tons of global annual production serves as an important building block and organic synthon for the synthesis of fine chemicals,polystyrene plastics,and elastomers.Thus,in the past decades,many direct transformations of this costless styrene feedstock were disclosed for the preparation of high-value chemicals,which to date,generally performed on the functionalization of styrenes through the allylic C-H bond,C(sp2)-H bond,or the C=C double bond cleavage.However,the dealkenylative functionalization of styrenes via the direct C-C single bond cleavage is so far challenging and still unknown.Herein,we report the novel and efficient C-C amination and hydroxylation reactions of styrenes for the synthesis of valuable aryl amines and phenols via the site-selective C(Ar)-C(alkenyl)single bond cleavage.This chemistry unlocks the new transformation and application of the styrene feedstock and provides an efficient protocol for the late-stage modification of substituted styrenes with the site-directed dealkenylative amination and hydroxylation.
基金Financial supports were provided by the National Key R&D Program of China(2021YFA1500200 and 2021YFF0701600)the NSFC(22271249)the Fundamental Research Funds for the Central Universities(226-2022-00224 and 226-2023-00115).
文摘Here,we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity.This difunctionalization reaction could undergo smoothly using 1 mol%catalyst loading with good functional group tolerance.Not only di-and tri-substituted hydrosilanes,but also alkoxysilane is suitable,which does explore the scope of the family of 1-amino-2-silyl compounds.The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot,two-step transformations.The primary mechanism has been proposed based on the control experiments.
基金We gratefully acknowledge the financial support from the National Natural Science Foundation of China(Nos.21772202,21701073,21831008)Beijing Municipal Science&Technology Commission(No.Z181100004218004)+1 种基金Beijing National Laboratory for Molecular Sciences(No.BNLMS-CXXM-201901)the Fundamental Research Funds for the Central Universities(lzujbky-2017-12 and lzujbky-2019-kb06).
文摘Summary of main observation and conclusion Herein,unprecedented rhenium-catalyzed decarboxylative oxytri-/difluoromethylation and Heck-type trifluoromethylation of styrenes have been developed by using hypervalent iodine(Ⅲ)reagents derived from cheap,stable,and easy-handling fluorinated carboxylic acids.Mechanistic studies revealed a radical decarboxylative trifluoromethylation pathway occurring in these reactions.
