The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the ...The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.展开更多
Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoall...Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoallenylsilane derivatives in high yields with excellent regioselectivities.This protocol featured good functional group compatibility and broad substrate scopes,enabling the formation of C-Si bond under cheap copper catalyst with a low loading.Furthermore,this means showed potential application value in the late-stage functionalization of natural products.展开更多
Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformat...Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.展开更多
Selective 3-cyanation of indoles was achieved under heterogeneous catalysis of Ru（III）-exchanged NaY zeolite （RuY） as a recyclable catalyst, in combination with K4[Fe（CN）6] as a nontoxic, slow cyanide releasing ...Selective 3-cyanation of indoles was achieved under heterogeneous catalysis of Ru（III）-exchanged NaY zeolite （RuY） as a recyclable catalyst, in combination with K4[Fe（CN）6] as a nontoxic, slow cyanide releasing agent. Under the aforementioned conditions, good yields of the desired products were obtained.展开更多
Current studies on the oxidative C--H functionalization of benzylic ethers for C--C forging process dominantly focus on primary ethers. The corresponding reaction of secondary ethers remains underdeveloped. Herein, a ...Current studies on the oxidative C--H functionalization of benzylic ethers for C--C forging process dominantly focus on primary ethers. The corresponding reaction of secondary ethers remains underdeveloped. Herein, a practical and efficient oxidative C--H cyanation of secondary benzylic ethers with TMSCN in the presence of DDQ is described. The metal-free process is well tolerated with a wide variety of electronically varied α-monosubstituted isochromans, facilely furnishing a library of isochromans bearing α-aryl α-cyano substituent patterns for further diversification and bioactive small molecule identification.展开更多
Nitrile compounds are a class of high-value chemicals and versatile intermediates which can easily be transformed into a variety of useful products bearing functional groups such as carboxyl, carbamoyl, aminomethyl, k...Nitrile compounds are a class of high-value chemicals and versatile intermediates which can easily be transformed into a variety of useful products bearing functional groups such as carboxyl, carbamoyl, aminomethyl, ketyl and heterocyclic derivatives. Various thermal catalytic cyanation procedures have been devised and scaled up industrially while developing alternative methods are actively pursued. The access to these classes of molecules electrochemically offers greener alternatives to their preparation. The development of electrochemical synthesis of cyano-containing compounds under mild conditions with low energy consumption will imminently become indispensable approaches for industrial production of nitriles. The electrochemical cyanation presents many challenges from the toxicity of cyanide to the development of catalysts and the design of electrochemical cells. Electrochemical cyanation reaction offers promise to conveniently accessing nitriles but still requires efficient electro-catalysts, safe protocols and scale up considerations. This review discusses recent progress in the field of electrochemical synthesis of nitrile compounds placing emphasis on electro-synthetic and electro-catalytic mechanism aspects while making reference to original works to highlight the progress in this area.展开更多
Aminonitriles were prepared efficiently from anodic cyanation of ?amino ester. The effect of different solvents and electrolytes was studied. The other byproducts were analyzed.
Chiral bisoxazoline(box)ligands with indene groups at C4 and C5 are highly potent in asymmetric catalysis,but face challenges in terms of cost and recyclability.To address this,we have designed polystyrene-supported b...Chiral bisoxazoline(box)ligands with indene groups at C4 and C5 are highly potent in asymmetric catalysis,but face challenges in terms of cost and recyclability.To address this,we have designed polystyrene-supported box ligands by modifying the indene moiety instead of the traditional methylene bridge.This design preserves the necessary steric environment for copper coordination,enabling high efficiency and excellent enantioselectivity as examined in photoinduced asymmetric cyanation reactions.The resulting copper complexes are robust and recyclable,maintaining performance over five cycles.This approach provides a sustainable and practical solution for asymmetric catalysis with chiral box ligands.展开更多
Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)ca...Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.展开更多
A copper-catalyzed cyanation/diarylmethylation of formamides has been developed for the synthesis ofα-cyano functionalized tetra-substituted olefins by utilizing para-quinone methides(p-QMs)and trimethylcyanosilane a...A copper-catalyzed cyanation/diarylmethylation of formamides has been developed for the synthesis ofα-cyano functionalized tetra-substituted olefins by utilizing para-quinone methides(p-QMs)and trimethylcyanosilane as functionalization sources.Various kinds of p-QMs and formamides are well tolerated,delivering the desired products with 72%—94%yields,demonstrating broad functional group tolerance.Notably,the reaction does not require noble metals and proceeds regioselectively under mild conditions.Based on step-by-step control experiments,Hammett studies and DFT calculation,a plausible mechanism is proposed.展开更多
A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHP...A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.展开更多
The transition-metal-catalyzed migratory functionalization has emerged as a robust protocol for the building of C–C bonds remote from the“initiation”position.However,a similar strategy for the construction of quate...The transition-metal-catalyzed migratory functionalization has emerged as a robust protocol for the building of C–C bonds remote from the“initiation”position.However,a similar strategy for the construction of quaternary carbon centers is still underdeveloped and only a limited number of reports exist.Herein,we report a nickel-catalyzed migratory hydrocyanation of unconjugated dienes to construct remote cyano-substituted quaternary carbon centers.This transformation features exceptional regioselectivity,mild reaction conditions,broad substrate scope and high yields.The synthetic utility of this method has been highlighted by a series of product derivatizations,and the potential of this transformation has been extended to synthesize TRPV1 antagonist and the key intermediate in the total synthesis of quebrachamine.Density functional theory(DFT)studies unveiled that the specific catalytic pocket assumed a significant role in the selective formation of cyano-substituted quaternary carbon centers.展开更多
Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-ec...Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-economic synthesis.Undoubtedly,selectively activating and transforming multiple inert chemical bonds is an even more intriguing and demanding task in synthetic chemistry.However,due to its inherent complexity and extreme challenges,this endeavour is rarely accomplished.We report a copper-mediated complete cleavage and selective transformation of multiple inert chemical bonds of three easily available feedstocks,i.e.,a sp^(2)C—H bond in indoles,three sp^(3)C—H bonds and one C—N bond in a methyl carbon atom in TMEDA,and the C≡N triple bond in CH_(3)CN.This reaction proceeds via tandem carbon and nitrogen atom transfer,and allows for the direct and efficient cyanation of indoles,presenting a simple and direct alternative for synthesizing 3-cyanoindoles.展开更多
The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generall...The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful.The challenge in this significant transformation is the strong affinity of cyanide for metals,which hampers oxidative addition(OD)and reductive elimination(RE)making organometallic catalysis elusive.Herein,we demonstrate for the first time that photoredox-nickel-catalyzed cyanations of aryl halides are readily enabled by visible light,in which Ni(Ⅱ)species are transiently oxidized to Ni(Ⅲ)species,thereby facilitating subsequent cyanide transfer and RE.Using this dual catalysis strategy,we cyanated aryl and alkenyl halides at room temperature in a highly benign manner(30 examples,53-93% yield)by avoiding the use of air-sensitive ligands,Ni(0)precursors,and hypertoxic cyanation reagents,while also limiting excess metal waste.Computational studies were also used to help understand the present transformation.展开更多
With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Liu Guosheng(刘国生)at Shanghai Institute of Organic Chemistry,Chinese Academy of ...With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Liu Guosheng(刘国生)at Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,and Prof.Shannon Stahl at the University of Wisconsin-Madison,discovered a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C—H bonds展开更多
A ligand-accelerated, branch-selective oxidative cyanation of alkenes has been developed in the presence of catalytic Cu_2O.Both styrenes and aliphatic alkenes with directing groups are well tolerated in this inexpens...A ligand-accelerated, branch-selective oxidative cyanation of alkenes has been developed in the presence of catalytic Cu_2O.Both styrenes and aliphatic alkenes with directing groups are well tolerated in this inexpensive protocol.The mild condition allows for a good tolerance of functional groups, enabling facile access to a diverse array of simple and complex branched vinyl nitriles.The wide synthetic utility of this methodology has been further demonstrated via the efficient scaleup in both batch and continuous flow processes.展开更多
A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, provid- ing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.
A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich an...A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.展开更多
Aromatic nitriles were synthesized through copper-catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source.A series of functional groups were tolerated under the reaction conditions to pro...Aromatic nitriles were synthesized through copper-catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source.A series of functional groups were tolerated under the reaction conditions to provide the products in good yields.Moreover,this protocol avoids using of highly toxic alkali cyanides and expensive palladium catalysts.展开更多
The cyanation-esterification reaction of a-keto esters catalysed by N-heterocyclic carbenes （NHCs） is developed Under the catalysis of 10 tool% 1,3-bis（2,6-diisopropylphenyl）imidazol-2-ylidene, aromatic and alipha...The cyanation-esterification reaction of a-keto esters catalysed by N-heterocyclic carbenes （NHCs） is developed Under the catalysis of 10 tool% 1,3-bis（2,6-diisopropylphenyl）imidazol-2-ylidene, aromatic and aliphatic a-keto esters reacted with ethyl cyanoformate or acetyl cyanide to produce the corresponding cyano esters with a tetra- substituted carbon center in high yields.展开更多
基金the National Natural Science Foundation of China(Nos.22072167,22202218)the Jiangsu Natural Science Funds for Young Scholar(No.BK20211093)is greatly appreciated.
文摘The selective conversion of CO_(2)and NH_(3)into valuable nitriles presents significant potential for CO_(2)utilization.In this study,we exploited the synergistic interplay between silicon and fluoride to augment the nickel-catalyzed reductive cyanation of aryl pseudohalides containing silyl groups,utilizing CO_(2)and NH_(3)as the CN source.Our methodology exhibited exceptional compatibility with diverse functional groups,such as alcohols,ketones,ethers,esters,nitriles,olefins,pyridines,and quinolines,among others,as demonstrated by the successful synthesis of 58 different nitriles.Notably,we achieved high yields in the preparation of bifunctionalized molecules,including intermediates for perampanel,derived from osilylaryl triflates,which are well-known as aryne precursors.Remarkably,no degradation of substrates or formation of aryne intermediates were observed.Mechanistic studies imply that the formation of pentacoordinated silyl isocyanate intermediates is crucial for the key C-C coupling step and the presence of vicinal silyl group in the substrate is beneficial to further make this step kinetically favorable.
基金support of this work by the funding of the National Natural Science Foundation of China(No.22371269)the State Key Laboratory of Elementoorganic Chemistry Nankai University(No.202001)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0450301)the Open Project of Key Laboratory of Organosilicon Chemistry,and Material Technology of Ministry of Education,Hangzhou Normal University(No.KFJJ2022013)。
文摘Herein,we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes,which provided an efficient method to access CN-bearing tri-and tetrasubstituted homoallenylsilane derivatives in high yields with excellent regioselectivities.This protocol featured good functional group compatibility and broad substrate scopes,enabling the formation of C-Si bond under cheap copper catalyst with a low loading.Furthermore,this means showed potential application value in the late-stage functionalization of natural products.
基金Financial support from National Key R&D Program of China(No.2023YFA1507203)National Natural Science Foundation of China(Nos.22371149,22188101)+2 种基金the Fundamental Research Funds for the Central Universities(No.63224098)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Herein,a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution(S_(N)Ar) using TMSCN as a cheap cyanide source under mild conditions has been presented.This transformation utilizes commercially available reagents,cheap electrodes,and simple equipment.Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope,excellent functional group tolerance,and selective C-O bond cleavage.Furthermore,late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy.Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation,and undergoing the followed S_(N)Ar process.
文摘Selective 3-cyanation of indoles was achieved under heterogeneous catalysis of Ru（III）-exchanged NaY zeolite （RuY） as a recyclable catalyst, in combination with K4[Fe（CN）6] as a nontoxic, slow cyanide releasing agent. Under the aforementioned conditions, good yields of the desired products were obtained.
基金financial supported by the National Natural Science Foundation of China(No. 21722204)Fok Ying Tung Education Foundation(No. 151035)the Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University) (No. CHEMR2016-B09)
文摘Current studies on the oxidative C--H functionalization of benzylic ethers for C--C forging process dominantly focus on primary ethers. The corresponding reaction of secondary ethers remains underdeveloped. Herein, a practical and efficient oxidative C--H cyanation of secondary benzylic ethers with TMSCN in the presence of DDQ is described. The metal-free process is well tolerated with a wide variety of electronically varied α-monosubstituted isochromans, facilely furnishing a library of isochromans bearing α-aryl α-cyano substituent patterns for further diversification and bioactive small molecule identification.
基金supports from the National Natural Science Foundation of China(22022204,21633013)the Natural Science Foundation of Jiangsu Province(BK20180248).
文摘Nitrile compounds are a class of high-value chemicals and versatile intermediates which can easily be transformed into a variety of useful products bearing functional groups such as carboxyl, carbamoyl, aminomethyl, ketyl and heterocyclic derivatives. Various thermal catalytic cyanation procedures have been devised and scaled up industrially while developing alternative methods are actively pursued. The access to these classes of molecules electrochemically offers greener alternatives to their preparation. The development of electrochemical synthesis of cyano-containing compounds under mild conditions with low energy consumption will imminently become indispensable approaches for industrial production of nitriles. The electrochemical cyanation presents many challenges from the toxicity of cyanide to the development of catalysts and the design of electrochemical cells. Electrochemical cyanation reaction offers promise to conveniently accessing nitriles but still requires efficient electro-catalysts, safe protocols and scale up considerations. This review discusses recent progress in the field of electrochemical synthesis of nitrile compounds placing emphasis on electro-synthetic and electro-catalytic mechanism aspects while making reference to original works to highlight the progress in this area.
文摘Aminonitriles were prepared efficiently from anodic cyanation of ?amino ester. The effect of different solvents and electrolytes was studied. The other byproducts were analyzed.
基金the National Natural Science Foundation of China(Nos.92256301,22371085,22271113,22471089)the National Key R&D Program of China(Nos.2023YFA1507203,2024YFA1509700)+4 种基金the Fundamental Research Funds for the Central Universities(No.CCNU24JCPT018)the Wuhan Natural Science Foundation(No.2024040801020303)the Postdoctor Project of Hubei Province under Grant Number 2024HBBHCXB039the China Postdoctoral Science Foundation(No.2024M751614)First Batch of Postdoctoral Overseas Talent Program of China for support of this research.
文摘Chiral bisoxazoline(box)ligands with indene groups at C4 and C5 are highly potent in asymmetric catalysis,but face challenges in terms of cost and recyclability.To address this,we have designed polystyrene-supported box ligands by modifying the indene moiety instead of the traditional methylene bridge.This design preserves the necessary steric environment for copper coordination,enabling high efficiency and excellent enantioselectivity as examined in photoinduced asymmetric cyanation reactions.The resulting copper complexes are robust and recyclable,maintaining performance over five cycles.This approach provides a sustainable and practical solution for asymmetric catalysis with chiral box ligands.
基金supported by the Guangxi Science and Technology Major Program(Guike AA24263012)the National Natural Science Foundation of China(22471046,22301048,22201049)the Bagui Outstanding Youth Talent Project。
文摘Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.
基金supported by the Natural Science Foundation of Hunan Province(2023JJ30274,2023JJ30275)Scientific Research Fund of Hunan Provincial Education Department(23A0497,23B0634)+1 种基金National Natural Science Foundation of China(22308116)Basic and Applied Basic Research Foundation of Guangdong Province(2022A1515110118).
文摘A copper-catalyzed cyanation/diarylmethylation of formamides has been developed for the synthesis ofα-cyano functionalized tetra-substituted olefins by utilizing para-quinone methides(p-QMs)and trimethylcyanosilane as functionalization sources.Various kinds of p-QMs and formamides are well tolerated,delivering the desired products with 72%—94%yields,demonstrating broad functional group tolerance.Notably,the reaction does not require noble metals and proceeds regioselectively under mild conditions.Based on step-by-step control experiments,Hammett studies and DFT calculation,a plausible mechanism is proposed.
基金supported by the National Natural Science Foundation of China(22201087)the National Key R&D Program of China(2022YFA1503200)Guangdong Basic and Applied Basic Research Foundation(2022A1515012507)。
文摘A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.
基金the National Natural Science Foundation of China(22278265,U22B20137 and 22203069)the Zhejiang Provincial Natural Science Foundation of China(LR24B020002)+1 种基金the start-up funding from Hangzhou Normal University(4095C50222204165 and 4095C50223204074)the Interdisciplinary Research Project of Hangzhou Normal University(2024JCXK04)for financial support of this research。
文摘The transition-metal-catalyzed migratory functionalization has emerged as a robust protocol for the building of C–C bonds remote from the“initiation”position.However,a similar strategy for the construction of quaternary carbon centers is still underdeveloped and only a limited number of reports exist.Herein,we report a nickel-catalyzed migratory hydrocyanation of unconjugated dienes to construct remote cyano-substituted quaternary carbon centers.This transformation features exceptional regioselectivity,mild reaction conditions,broad substrate scope and high yields.The synthetic utility of this method has been highlighted by a series of product derivatizations,and the potential of this transformation has been extended to synthesize TRPV1 antagonist and the key intermediate in the total synthesis of quebrachamine.Density functional theory(DFT)studies unveiled that the specific catalytic pocket assumed a significant role in the selective formation of cyano-substituted quaternary carbon centers.
基金support from the National Natural Science Foundation of China(Grant Nos.22378106,21878072,21706058,and 22002169)the Natural Science Foundation of Hunan Province(Grant No.2020JJ2011)the China Postdoctoral Science Foundation(No.2019M662774).
文摘Comprehensive Summary The activation of inert chemical bonds is an exciting area of research in chemistry because it enables the direct utilization of readily available starting materials and promotes atom-and step-economic synthesis.Undoubtedly,selectively activating and transforming multiple inert chemical bonds is an even more intriguing and demanding task in synthetic chemistry.However,due to its inherent complexity and extreme challenges,this endeavour is rarely accomplished.We report a copper-mediated complete cleavage and selective transformation of multiple inert chemical bonds of three easily available feedstocks,i.e.,a sp^(2)C—H bond in indoles,three sp^(3)C—H bonds and one C—N bond in a methyl carbon atom in TMEDA,and the C≡N triple bond in CH_(3)CN.This reaction proceeds via tandem carbon and nitrogen atom transfer,and allows for the direct and efficient cyanation of indoles,presenting a simple and direct alternative for synthesizing 3-cyanoindoles.
基金the National Science Foundation of China(nos.21822103,21820102003,21822303,21772052,21772053,and 91956201)the Program of Introducing Talents of Discipline to Universities of China(111 Program,B17019)the Natural Science Foundation of Hubei Province(no.2017AHB047).
文摘The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful.The challenge in this significant transformation is the strong affinity of cyanide for metals,which hampers oxidative addition(OD)and reductive elimination(RE)making organometallic catalysis elusive.Herein,we demonstrate for the first time that photoredox-nickel-catalyzed cyanations of aryl halides are readily enabled by visible light,in which Ni(Ⅱ)species are transiently oxidized to Ni(Ⅲ)species,thereby facilitating subsequent cyanide transfer and RE.Using this dual catalysis strategy,we cyanated aryl and alkenyl halides at room temperature in a highly benign manner(30 examples,53-93% yield)by avoiding the use of air-sensitive ligands,Ni(0)precursors,and hypertoxic cyanation reagents,while also limiting excess metal waste.Computational studies were also used to help understand the present transformation.
文摘With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Liu Guosheng(刘国生)at Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,and Prof.Shannon Stahl at the University of Wisconsin-Madison,discovered a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C—H bonds
基金supported by the National Natural Science Foundation of China (21702029)the ‘‘Thousand Plan" Youth programthe Shanghai Sailing Program (17YF1400100)
文摘A ligand-accelerated, branch-selective oxidative cyanation of alkenes has been developed in the presence of catalytic Cu_2O.Both styrenes and aliphatic alkenes with directing groups are well tolerated in this inexpensive protocol.The mild condition allows for a good tolerance of functional groups, enabling facile access to a diverse array of simple and complex branched vinyl nitriles.The wide synthetic utility of this methodology has been further demonstrated via the efficient scaleup in both batch and continuous flow processes.
基金We thank the National Natural Science Foundation of China （No. 21272178）, the Natural Science Founda- tion of Zhejiang Province （Nos. R4110294 and LY12B02010）.
文摘A new copper and silver-mediated cyanation of aryl iodides with DDQ as a cyanide source is achieved, provid- ing nitriles with good yields. This new approach represents a safe method leading to aryl nitriles.
文摘A method for the efficient and reliable synthesis of aryl nitriles via the Cu20-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and defi- cient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halo- gen-free Cu20 as catalysts make the protocol an appealing option for aryl cyanations.
基金This project was financially supported by the National Natural Science Foundation of China(No.21302014)the Natural Science Foundation for Colleges and Universities of Jiangsu Province(13KJB150002)the Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(grant No.BM2012110).
文摘Aromatic nitriles were synthesized through copper-catalyzed cyanations of aromatic bromides using benzoyl cyanide as the cyanide source.A series of functional groups were tolerated under the reaction conditions to provide the products in good yields.Moreover,this protocol avoids using of highly toxic alkali cyanides and expensive palladium catalysts.
文摘The cyanation-esterification reaction of a-keto esters catalysed by N-heterocyclic carbenes （NHCs） is developed Under the catalysis of 10 tool% 1,3-bis（2,6-diisopropylphenyl）imidazol-2-ylidene, aromatic and aliphatic a-keto esters reacted with ethyl cyanoformate or acetyl cyanide to produce the corresponding cyano esters with a tetra- substituted carbon center in high yields.
