The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediat...The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediated fluoroalkyl-mono/disulfuration of unactivated alkenes with high efficiency and high selectivity.A wide range of terminal and internal alkenes are good coupling partners,affording the expected products in moderate to good yields(>90 examples).The exceedingly mild reaction conditions,exceptional functional group tolerance,broad substrate scope,and the potential for late-stage modifications of pharmaceutical molecules highlight the utility of this method in the preparation of privileged motifs from readily available disulfides,tetrasulfides,and diselenides.Mechanistic studies suggest that a secondary alkyl radical intermediate undergoes efficient homolytic substitution with disulfides,facilitating the modular synthesis of a diverse array of unsymmetrical thioethers.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
Although fluorobis(phenylsulfonyl)methane(FBSM)and its cyclic analog 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide(FBDT)possess similar physicochemical properties,Shibata et al.found that FBSM failed to undergo nucleo...Although fluorobis(phenylsulfonyl)methane(FBSM)and its cyclic analog 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide(FBDT)possess similar physicochemical properties,Shibata et al.found that FBSM failed to undergo nucleophilic monofluoromethylation of aldehydes regardless of the reaction conditions at-tempted(using various organic and inorganic bases).However,it was later discovered by Hu et al.that the nucleophilic monofluoromethylation could be accomplished by employing lithium hexamethyldisi-lazide(LiHMDS)as a base.Herein,we present an in-depth computational investigation into the intrigu-ing effects of reagent structure and bases on the nucleophilic monofluoromethylation of aldehydes.The computations reveal the 1,4-diazabicyclo[2.2.2]octane(DABCO)catalyzed nucleophilic monofluoromethy-lation of benzaldehyde with acyclic FBSM is a thermodynamically unfavorable process mainly due to the destabilizing O···O lone pair repulsions in FBSM product,whereas such repulsion could be largely avoided in FBDT product because of its constrained five-membered ring structure.Employing LiHMDS as a base can not only facilitate the nucleophilic monofluoromethylation via Li–O interactions but also render the monofluoromethylation of benzaldehyde with FBSM thermodynamically favored.展开更多
Herein, we report an unprecedented regiospecific oxidative Mizoroki-Heck type reaction for the synthesis of α-difluoromethyl homoallylic alcohols. The reaction shows broad substrate scopes and high functional group t...Herein, we report an unprecedented regiospecific oxidative Mizoroki-Heck type reaction for the synthesis of α-difluoromethyl homoallylic alcohols. The reaction shows broad substrate scopes and high functional group tolerance. Late-stage functionalization of complex biologically active molecules demonstrates the synthetic potential of this transformation. Mechanistic study supports the involvement of MnBr_(2) catalyzed radical 1,2-silyl transfer.展开更多
Herein,the Nd@g-C_(3)N_(4) dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R_(f)SO_(2)Cl under visible-light and ultrasound conditions was firstly reported.The photogenerated el...Herein,the Nd@g-C_(3)N_(4) dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R_(f)SO_(2)Cl under visible-light and ultrasound conditions was firstly reported.The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation.A wide range of N-heteroarenes,alkenes and R_(f)SO_(2)Cl,were well compatible for this reaction to access valuable fluoroalkylated N-heteroarenes with diverse structural features.The antitumor potential of synthesized fluoroalkylated N-heterocycles against Glioma 261 cells was evaluated by CCK8 assay.Notably,compound 4 aka demonstrated remarkable efficacy,exhibiting approximately sevenfold greater potency than temozolomide,a widely used chemotherapeutic agent.展开更多
We herein described an efficient and practical protocol for radical cyclization of aryl alkynoates to access 3-fluoroalkyl-substituted coumarins using readily available,easy-to-handle and low-cost fluoroalkyl carboxyl...We herein described an efficient and practical protocol for radical cyclization of aryl alkynoates to access 3-fluoroalkyl-substituted coumarins using readily available,easy-to-handle and low-cost fluoroalkyl carboxylic anhydride as fluoroalkyl source.This method is featured by its generally applicable to several kinds of fluoroalkyl carboxylic anhydrides including difluoromethy1,trifluoromethyl,pentafluoroethyl,heptafluoropropyl and chlorodifluoromethyl,as well as a good functional group tolerance with respect to a wide variety of aryl alkynoates.This reaction was triggered by addition of fluoroalkyl radical to the triple bond of alkynoates,followed by a cascade 5-exo cyclization/oxidization/1,2-ester migration/rearomatization process.展开更多
The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the fie...The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the field of organofluorine chemistry and have thus made significant contributions.Furthermore,these newly developed methods are typically safer and more effective than the traditional methods.In this review,wewill summarize the representative contributions of new reagents and reactions developed in the past decade.展开更多
A series of spiro compounds have been synthesized via several steps. The structure of these compounds were confirmed by ^1H NMR, 13C NMR, IR, MS spectra and X-ray diffraction analysis. The possible mechanism to form t...A series of spiro compounds have been synthesized via several steps. The structure of these compounds were confirmed by ^1H NMR, 13C NMR, IR, MS spectra and X-ray diffraction analysis. The possible mechanism to form these products was also proposed.展开更多
Ⅰ. INTRODUCTION Perfluoroalkylation of alkenes is one of the most important methods for industrial as well as laboratory syntheses of a variety of organofluorine compounds. It is usually induced by light, heat or rad...Ⅰ. INTRODUCTION Perfluoroalkylation of alkenes is one of the most important methods for industrial as well as laboratory syntheses of a variety of organofluorine compounds. It is usually induced by light, heat or radical initiators. A few of transition metals and their complexes have been shown to be able to catalyse the addition reaction展开更多
A general and broadly applicable copper and photoredox dual-catalyzed multicomponent 1,4-perfluoroalkylcyanation of 1,3-enynes has been developed.This protocol enjoys success with high regioselectivity,mild reaction c...A general and broadly applicable copper and photoredox dual-catalyzed multicomponent 1,4-perfluoroalkylcyanation of 1,3-enynes has been developed.This protocol enjoys success with high regioselectivity,mild reaction conditions,and excellent functional-group tolerance,allowing the facile synthesis of structurally diverse perfluoroalkylated allenes from readily available fluoroalkyl halides,1,3-enynes and TMscN in a one-pot manner.A reasonable mechanism has been proposed according to a series of control experiments.展开更多
Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoi...Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.展开更多
An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides ar...An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides are used,the substitution products are obtained in moderate to excellent yields.The prepared difluoro(phenylsulfonimidoyl)methylated alkanes can be readily transformed to gem-difluoroalkenes via base-mediatedβ-elimination reaction.展开更多
The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of ...The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of fluoroalkyl groups into the chemical skeletons can cause considerable alternations in the chemical, physical and biological properties of molecules, which has attracted numerous scientists from different fields. This review focuses on N-heterocyclic carbene(NHC)-catalyzed fluoroalkylation reactions, providing a detailed analysis and summary of the achievements in the past two decades. Many successful examples clearly indicate that NHCs can catalyze the tranformation of fluoroalkylation reagents with various electronic characteristics, whether electrophilic, nucleophilic, or radical precursors. Herein, the fluoroalkylation reactions are classified based on different catalytic modes of NHCs: Lewis base catalysis, Umploung catalysis, radical catalysis and others. Meanwhile, by refining and systematically studying the contribution of NHC catalysis in fluoroalkylation reactions, this review is expected to provide valuable insights and enlightenment for related fields.展开更多
A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can...A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can generate both difluoromethyl radical(·CF_(2)H)and difluorocarbene(:CF_(2))intermediates.Thus,a variety of fluoroalkylation transformations havebeen achieved by·CF_(2)H,such asoxidativedifluoromethylation of electron-deficient heterocycles,nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides,and photoredox difluoromethylation of alkenes,or by:CF_(2),such as gem-difluorocyclopropanation of alkenes,base-promoted difluoromethylation of heteroatom nucleophiles,Pd-catalyzed difluoromethylation of arylboronic acids,and Cu-mediated trifluoromethylation of aryl iodides(via:CF_(2) and recombined CF_(3)-).These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.展开更多
Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic mo...Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic molecules.Transition-metal-mediated cross-electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents.Moreover,alkenes or alkynes-involved three-component cross-electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes.Herein,we comprehensively summarize the transition-metal-mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective,including trifluoromethylation,difluoroalkylation,monofluoroalkylation,and so on.Different transition metals(Cu,Ni,etc.)and strategies are discussed,in which nickel-catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site-selectively access organofluorine compounds.展开更多
Addition of fluoroalkyl iodides to olefins in the presence of hydrogen peroxide(H_2O_(?)) in acetone,acetonitrile or ethanol gave the corresponding 1:1 adducts in good yields.Reaction of fluoroalkyl iodide with dially...Addition of fluoroalkyl iodides to olefins in the presence of hydrogen peroxide(H_2O_(?)) in acetone,acetonitrile or ethanol gave the corresponding 1:1 adducts in good yields.Reaction of fluoroalkyl iodide with diallyl ether(DAE)yielded tetrahydrofuran derivatives,p-Hydroquinone (p-HQ)can partly suppress the reaction.A radical initiation mechanism is proposed.展开更多
文摘The accompanied forge of C(sp^(3))–S and C(sp^(3))–C(sp^(3))bonds across alkene frameworks serves as a potent strategy to construct biologically important compounds.Here,we report a metal-free,photochemically mediated fluoroalkyl-mono/disulfuration of unactivated alkenes with high efficiency and high selectivity.A wide range of terminal and internal alkenes are good coupling partners,affording the expected products in moderate to good yields(>90 examples).The exceedingly mild reaction conditions,exceptional functional group tolerance,broad substrate scope,and the potential for late-stage modifications of pharmaceutical molecules highlight the utility of this method in the preparation of privileged motifs from readily available disulfides,tetrasulfides,and diselenides.Mechanistic studies suggest that a secondary alkyl radical intermediate undergoes efficient homolytic substitution with disulfides,facilitating the modular synthesis of a diverse array of unsymmetrical thioethers.
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supported by the Natural Science Foundation of China(Nos.22122104,21933004 and 21702098).
文摘Although fluorobis(phenylsulfonyl)methane(FBSM)and its cyclic analog 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide(FBDT)possess similar physicochemical properties,Shibata et al.found that FBSM failed to undergo nucleophilic monofluoromethylation of aldehydes regardless of the reaction conditions at-tempted(using various organic and inorganic bases).However,it was later discovered by Hu et al.that the nucleophilic monofluoromethylation could be accomplished by employing lithium hexamethyldisi-lazide(LiHMDS)as a base.Herein,we present an in-depth computational investigation into the intrigu-ing effects of reagent structure and bases on the nucleophilic monofluoromethylation of aldehydes.The computations reveal the 1,4-diazabicyclo[2.2.2]octane(DABCO)catalyzed nucleophilic monofluoromethy-lation of benzaldehyde with acyclic FBSM is a thermodynamically unfavorable process mainly due to the destabilizing O···O lone pair repulsions in FBSM product,whereas such repulsion could be largely avoided in FBDT product because of its constrained five-membered ring structure.Employing LiHMDS as a base can not only facilitate the nucleophilic monofluoromethylation via Li–O interactions but also render the monofluoromethylation of benzaldehyde with FBSM thermodynamically favored.
基金the National Natural Science Foundation of China (No. 21901191)the Fundamental Research Funds for the Central Universities and Wuhan University for financial support
文摘Herein, we report an unprecedented regiospecific oxidative Mizoroki-Heck type reaction for the synthesis of α-difluoromethyl homoallylic alcohols. The reaction shows broad substrate scopes and high functional group tolerance. Late-stage functionalization of complex biologically active molecules demonstrates the synthetic potential of this transformation. Mechanistic study supports the involvement of MnBr_(2) catalyzed radical 1,2-silyl transfer.
基金financial support from Natural Science Foundation of Hunan Province(No.2025JJ50615)the Science and Technology Innovation Program of Hunan Province(No.2022RC4044)+2 种基金Hunan Provincial Health-Level Talent Scientific Research Project(No.R2023150)Clinical Research Center for Prevention and Treatment of Cognitive Impairment in Hunan Province(No.2023SK4050)University of South China Clinical Research 4310 Program(No.20224310NHYCG08)。
文摘Herein,the Nd@g-C_(3)N_(4) dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R_(f)SO_(2)Cl under visible-light and ultrasound conditions was firstly reported.The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation.A wide range of N-heteroarenes,alkenes and R_(f)SO_(2)Cl,were well compatible for this reaction to access valuable fluoroalkylated N-heteroarenes with diverse structural features.The antitumor potential of synthesized fluoroalkylated N-heterocycles against Glioma 261 cells was evaluated by CCK8 assay.Notably,compound 4 aka demonstrated remarkable efficacy,exhibiting approximately sevenfold greater potency than temozolomide,a widely used chemotherapeutic agent.
基金supported by the Natural Science Foundation of Fujian Province(No.2022J01500)the National Natural Science Foundation of China(No.22071241)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZZ105).
文摘We herein described an efficient and practical protocol for radical cyclization of aryl alkynoates to access 3-fluoroalkyl-substituted coumarins using readily available,easy-to-handle and low-cost fluoroalkyl carboxylic anhydride as fluoroalkyl source.This method is featured by its generally applicable to several kinds of fluoroalkyl carboxylic anhydrides including difluoromethy1,trifluoromethyl,pentafluoroethyl,heptafluoropropyl and chlorodifluoromethyl,as well as a good functional group tolerance with respect to a wide variety of aryl alkynoates.This reaction was triggered by addition of fluoroalkyl radical to the triple bond of alkynoates,followed by a cascade 5-exo cyclization/oxidization/1,2-ester migration/rearomatization process.
基金support from the National Natural Science Foundation of China(grant nos.21991121,21931013,21925105,22025103,and 21961142015)the National Key Research and Development Program of China(grant no.2021YFF0701700).
文摘The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the field of organofluorine chemistry and have thus made significant contributions.Furthermore,these newly developed methods are typically safer and more effective than the traditional methods.In this review,wewill summarize the representative contributions of new reagents and reactions developed in the past decade.
基金Project supported by the National Natural Science Foundation of China （No. 20472047）.
文摘A series of spiro compounds have been synthesized via several steps. The structure of these compounds were confirmed by ^1H NMR, 13C NMR, IR, MS spectra and X-ray diffraction analysis. The possible mechanism to form these products was also proposed.
文摘Ⅰ. INTRODUCTION Perfluoroalkylation of alkenes is one of the most important methods for industrial as well as laboratory syntheses of a variety of organofluorine compounds. It is usually induced by light, heat or radical initiators. A few of transition metals and their complexes have been shown to be able to catalyse the addition reaction
基金supported by the National Natural Science Foundation of China(Nos.22301256 and 22271244)the Hunan Provincial Natural Science Foundation of China(2023JJ40618)+1 种基金the Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University(2022c02)the Hunan Provincial Innovation Foundation for Postgraduate(CX20230644,XDCX2023Y162)
文摘A general and broadly applicable copper and photoredox dual-catalyzed multicomponent 1,4-perfluoroalkylcyanation of 1,3-enynes has been developed.This protocol enjoys success with high regioselectivity,mild reaction conditions,and excellent functional-group tolerance,allowing the facile synthesis of structurally diverse perfluoroalkylated allenes from readily available fluoroalkyl halides,1,3-enynes and TMscN in a one-pot manner.A reasonable mechanism has been proposed according to a series of control experiments.
基金financially supported by the National Natural Science Foundation of China (20825209, 20832008, 20772144)the Chinese Academy of Sciences (Hundreds-Talent Program and Knowledge Innovation Program)
文摘Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.
基金Support of our work by the National Basic Research Program of China(Nos.2012CB215500 and 2012CB821600)the NNSFC(No.21372246)+1 种基金Shanghai QMX program(No.13QH1402400)the Chinese Academy of Sciences is gratefully acknowledged.
文摘An efficient nucleophilic difluoro(phenylsulfonimidoyl)methylation of unactivated primary alkyl bromides with PhSO(NTBS)CF_(2)H has been developed.It is particularly remarkable that,when 1.5 equiv.of alkyl bromides are used,the substitution products are obtained in moderate to excellent yields.The prepared difluoro(phenylsulfonimidoyl)methylated alkanes can be readily transformed to gem-difluoroalkenes via base-mediatedβ-elimination reaction.
基金supported by the National Natural Science Foundation of China (21871160, 21672121, 22071130)the Bayer Investigator Fellowthe Fellowship of Tsinghua-Peking Center for Life Sciences (CLS)。
文摘The fluoroalkyl fragment plays a vital role in various fields such as pharmaceuticals and materials science, and has a significant impact on human life not only on the present but also in the future. The insertion of fluoroalkyl groups into the chemical skeletons can cause considerable alternations in the chemical, physical and biological properties of molecules, which has attracted numerous scientists from different fields. This review focuses on N-heterocyclic carbene(NHC)-catalyzed fluoroalkylation reactions, providing a detailed analysis and summary of the achievements in the past two decades. Many successful examples clearly indicate that NHCs can catalyze the tranformation of fluoroalkylation reagents with various electronic characteristics, whether electrophilic, nucleophilic, or radical precursors. Herein, the fluoroalkylation reactions are classified based on different catalytic modes of NHCs: Lewis base catalysis, Umploung catalysis, radical catalysis and others. Meanwhile, by refining and systematically studying the contribution of NHC catalysis in fluoroalkylation reactions, this review is expected to provide valuable insights and enlightenment for related fields.
基金supported by National Natural Science Foundation of China(grant no.21901196)the Natural Science Basic Research Plan in Shaanxi Province of China(grant nos.2020JQ-016 and 2021GXLH-Z-096)+1 种基金the Fundamental Research Funds for the Central Universities(grant no.xhj032021007-01)Xi’an Jiaotong University(grant no.71211920000001).
文摘A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can generate both difluoromethyl radical(·CF_(2)H)and difluorocarbene(:CF_(2))intermediates.Thus,a variety of fluoroalkylation transformations havebeen achieved by·CF_(2)H,such asoxidativedifluoromethylation of electron-deficient heterocycles,nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides,and photoredox difluoromethylation of alkenes,or by:CF_(2),such as gem-difluorocyclopropanation of alkenes,base-promoted difluoromethylation of heteroatom nucleophiles,Pd-catalyzed difluoromethylation of arylboronic acids,and Cu-mediated trifluoromethylation of aryl iodides(via:CF_(2) and recombined CF_(3)-).These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.
基金supported by the National Natural Science Foundation of China(21931013,21991122)the National Key R&D Program of China(2021YFF0701700)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000)the Science and Technology Commission of Shanghai Municipality(22JC1403500,21XD1404400).
文摘Organofluorine compounds have attracted substantial interest in life and materials sciences due to the unique properties of fluorine atom(s)that often change the physicochemical and biological properties of organic molecules.Transition-metal-mediated cross-electrophile coupling between carbon electrophiles and fluoroalkyl electrophiles has emerged as a straightforward and efficient route for the synthesis of a wide range of fluoroalkylated compounds because of its synthetic convenience without the tedious synthesis of organometallic reagents.Moreover,alkenes or alkynes-involved three-component cross-electrophile couplings provide rapid and effective access to carbonfunctionalized fluoroalkylated alkanes and alkenes.Herein,we comprehensively summarize the transition-metal-mediated reductive fluoroalkylation of diverse carbon electrophiles through a historical perspective,including trifluoromethylation,difluoroalkylation,monofluoroalkylation,and so on.Different transition metals(Cu,Ni,etc.)and strategies are discussed,in which nickel-catalyzed reductive fluoroalkylation reactions represent an attractive and efficient synthetic route to site-selectively access organofluorine compounds.
基金This project was supported by the National Natural Science Foundation of China.
文摘Addition of fluoroalkyl iodides to olefins in the presence of hydrogen peroxide(H_2O_(?)) in acetone,acetonitrile or ethanol gave the corresponding 1:1 adducts in good yields.Reaction of fluoroalkyl iodide with diallyl ether(DAE)yielded tetrahydrofuran derivatives,p-Hydroquinone (p-HQ)can partly suppress the reaction.A radical initiation mechanism is proposed.
