Gastric cancer is the third leading cause of cancer-related mortality and remains a major global health issue^([1]).Annually,approximately 479,000individuals in China are diagnosed with gastric cancer,accounting for a...Gastric cancer is the third leading cause of cancer-related mortality and remains a major global health issue^([1]).Annually,approximately 479,000individuals in China are diagnosed with gastric cancer,accounting for almost 45%of all new cases worldwide^([2]).展开更多
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
In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic s...Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic stability,lipophilicity,excellent chemical and thermal stability.Therefore,various synthetic strategies have been developed for the construction of fluoroalkyl-containing compounds,using highly active fluorinating reagents and fluorinated building blocks.Recently,the use of easily available and inexpensive trifluoroacetic anhydride(TFAA)and its anhydride analogues has attracted great attention to access numerous fluoroalkyl-containing compounds through cyclization and coupling reactions.In this review,we summarized the recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides as reagents.This review aims to provide a reference for researchers on how to develop new synthetic straregies of fluorine-containing organic compounds and achieve kilograms or even tons preparation of fluorine-containing organic compounds using fluoroalkyl anhydrides.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
A polyether diol poly[3-bromomethyl-3-tridecafluorooctyloxymethyloxetane]glycol(PFBOX 3) was prepared in 91% yield from ring opening polymerization of 3-bromomethyl-3-tridecafluorooctyloxymethyloxetane 2 which was der...A polyether diol poly[3-bromomethyl-3-tridecafluorooctyloxymethyloxetane]glycol(PFBOX 3) was prepared in 91% yield from ring opening polymerization of 3-bromomethyl-3-tridecafluorooctyloxymethyloxetane 2 which was derived from 3,3-dibromomethyloxetane 1 and 1H,1H,2H,2H-perfluorooctanol.The waterborne fluorinated polyurethane FPU was thus obtained by condensed polymerization of PFBOX 3 with isophoronediisocyanate(IPDI).The structure of FPU was characterized by Fourier transform infrared spectrometer(FTIR).FPU showed good thermal stability under 300℃.The surface properties of FPU were studied by applied on cotton fabric.The treated fabric surface showed excellent water repellent property as the contact angle reached 147°.On the other hand,the surface showed slightly oil repellent property as the contact angle for nujol droplet was 126°.展开更多
As very useful superficial mediflcation agents, the common long perfluoroalkyl -- containing agents are facing the ecological problems, such as persistence, bioacumulatlen, and/or toxicity in the environment. In order...As very useful superficial mediflcation agents, the common long perfluoroalkyl -- containing agents are facing the ecological problems, such as persistence, bioacumulatlen, and/or toxicity in the environment. In order to overcome the problems, we designed and synthesized a polyether dioi containing short perfluoroaikyl side chains, which was condensed with diisocyanate to form fluorine-containing aqueous polyurethane. This aqueous polyurethane was applied on cotton fabrics by conventional pad-dry-cure process. The treated cotton fabrics showed good water repellent property with the contact angle reached 131°, and also IXBSessed good washing durability.展开更多
Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-su...Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.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 sequential transformation of fluoroalkylated adducts obtained from ethyl 3-hydroxy-4-pentenoate with fluorinated iodides was reported. The dehydrohalogenation of adducts was favored to give fluoroalkylated unsaturat...A sequential transformation of fluoroalkylated adducts obtained from ethyl 3-hydroxy-4-pentenoate with fluorinated iodides was reported. The dehydrohalogenation of adducts was favored to give fluoroalkylated unsaturated β-hydroxy esters in the presence of triethylamine. And intramolecular SN42 reaction products, fluoroalkylated β,γ-epoxy esters, were obtained in 10% aqueous sodium carbonate solution.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
Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from...Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.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
Dipolar cycloaddition reactions of ethyl 2-hydropolyfluoroalk-2-enoates (1) with some nitrones were de-scribed. The reaction of 3,4-dihydroisoquinoline N-oxide (2) with 1 took place readily in methylene chloride at ro...Dipolar cycloaddition reactions of ethyl 2-hydropolyfluoroalk-2-enoates (1) with some nitrones were de-scribed. The reaction of 3,4-dihydroisoquinoline N-oxide (2) with 1 took place readily in methylene chloride at room temperature to give the corresponding 5-fluoroalkylisoxazolidines regioselectively as a mixture of two di-astereoisomers (trans and cis) in high yields, while longer reaction time and higher temperature were needed in the case of non-cyclic nitrones. Under similar conditions the reaction of quinoline N-oxide (14) with 1 did not give the expected adducts and a ring-opening product was obtained.展开更多
A convenient and direct per(poly)fluoroalkylmethyl-introducing cyclopropanation reaction was described. In the presence of CrCl3/Fe, per(poly)fluoroalkyl iodides reacted with diethyl allylmalonate and its analogs to g...A convenient and direct per(poly)fluoroalkylmethyl-introducing cyclopropanation reaction was described. In the presence of CrCl3/Fe, per(poly)fluoroalkyl iodides reacted with diethyl allylmalonate and its analogs to give per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives in high yields. This reaction was considered to proceed by two steps: radical addition followed by cyclopropanation.展开更多
The reaction of 3-（1-hydropolyfluoroalkenyl）-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was investigated. 7-Fluoroalkyl-2,3-dihydro- 1,4-diazepine[ 1,2-d]quinazolin- 11-ones 2, 2-fluoroalkylisoxazolo[3,2-b]...The reaction of 3-（1-hydropolyfluoroalkenyl）-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was investigated. 7-Fluoroalkyl-2,3-dihydro- 1,4-diazepine[ 1,2-d]quinazolin- 11-ones 2, 2-fluoroalkylisoxazolo[3,2-b]quinazolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane, hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.展开更多
Initiated by CrCl3/Fe redox couple, per(poly)fluoroalkyl iodides added to methyl a-acetylamino acrylate, giving B-per(poly)fluoroalkyl a-amino acid derivatives in good yields.
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
基金supported by the Natural Science Foundation of Shanghai(23ZR1463600)Shanghai Pudong New Area Health Commission Research Project(PW2021A-69)Research Project of Clinical Research Center of Shanghai Health Medical University(22MC2022002)。
文摘Gastric cancer is the third leading cause of cancer-related mortality and remains a major global health issue^([1]).Annually,approximately 479,000individuals in China are diagnosed with gastric cancer,accounting for almost 45%of all new cases worldwide^([2]).
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.
文摘In the presence of CrC13 /Fe bimetal couple,per(poly)fluoroalkyl iodides add to vinyl cyclopropane compounds giving addition-ring-opening products in good yields.
基金supported by the National Natural Science Foundation of China(Nos.21772022,and 22171124)Minjiang University(No.MJY21041)Fuzhou University.
文摘Fluoroalkyl-containing organic compounds have exhibited wide applications in the field of pharmaceuticals,agrochemicals and materials science due to their outstanding properties such as biological activity,metabolic stability,lipophilicity,excellent chemical and thermal stability.Therefore,various synthetic strategies have been developed for the construction of fluoroalkyl-containing compounds,using highly active fluorinating reagents and fluorinated building blocks.Recently,the use of easily available and inexpensive trifluoroacetic anhydride(TFAA)and its anhydride analogues has attracted great attention to access numerous fluoroalkyl-containing compounds through cyclization and coupling reactions.In this review,we summarized the recent advances in the synthesis of fluoroalkylated compounds using fluoroalkyl anhydrides as reagents.This review aims to provide a reference for researchers on how to develop new synthetic straregies of fluorine-containing organic compounds and achieve kilograms or even tons preparation of fluorine-containing organic compounds using fluoroalkyl anhydrides.
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Shanghai Municipal Scientific Committee,China (No. 08JC1400400)
文摘A polyether diol poly[3-bromomethyl-3-tridecafluorooctyloxymethyloxetane]glycol(PFBOX 3) was prepared in 91% yield from ring opening polymerization of 3-bromomethyl-3-tridecafluorooctyloxymethyloxetane 2 which was derived from 3,3-dibromomethyloxetane 1 and 1H,1H,2H,2H-perfluorooctanol.The waterborne fluorinated polyurethane FPU was thus obtained by condensed polymerization of PFBOX 3 with isophoronediisocyanate(IPDI).The structure of FPU was characterized by Fourier transform infrared spectrometer(FTIR).FPU showed good thermal stability under 300℃.The surface properties of FPU were studied by applied on cotton fabric.The treated fabric surface showed excellent water repellent property as the contact angle reached 147°.On the other hand,the surface showed slightly oil repellent property as the contact angle for nujol droplet was 126°.
基金Supported by the Programfor Changjiang Scholars and Innovative Research Teamin University (No.IRT0526)
文摘As very useful superficial mediflcation agents, the common long perfluoroalkyl -- containing agents are facing the ecological problems, such as persistence, bioacumulatlen, and/or toxicity in the environment. In order to overcome the problems, we designed and synthesized a polyether dioi containing short perfluoroaikyl side chains, which was condensed with diisocyanate to form fluorine-containing aqueous polyurethane. This aqueous polyurethane was applied on cotton fabrics by conventional pad-dry-cure process. The treated cotton fabrics showed good water repellent property with the contact angle reached 131°, and also IXBSessed good washing durability.
基金the National Natural Science Foundation of China(21871043,21961130376)Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH,20200801065GH)the Fundamental Research Funds for the Central Universities(2412019ZD001,2412019FZ006)。
文摘Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.
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project supported by the National Natural Science Foundation of China （NNSFC） （Nos. 20972050, 21172148）.
文摘A sequential transformation of fluoroalkylated adducts obtained from ethyl 3-hydroxy-4-pentenoate with fluorinated iodides was reported. The dehydrohalogenation of adducts was favored to give fluoroalkylated unsaturated β-hydroxy esters in the presence of triethylamine. And intramolecular SN42 reaction products, fluoroalkylated β,γ-epoxy esters, were obtained in 10% aqueous sodium carbonate solution.
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.
基金Project supported by the National Natural Science Foundation of China.
文摘Potassium fluoride on alumina was proved to be an efficient dehydrohalogenating agent for the synthesis of per(poly)fluoroalkyl substituted alkenes and alkynes. The reaction was simple, mild and the yields ranged from good to excellent.
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.
基金the National Natural Science Foundation of China (No. 20172065).
文摘Dipolar cycloaddition reactions of ethyl 2-hydropolyfluoroalk-2-enoates (1) with some nitrones were de-scribed. The reaction of 3,4-dihydroisoquinoline N-oxide (2) with 1 took place readily in methylene chloride at room temperature to give the corresponding 5-fluoroalkylisoxazolidines regioselectively as a mixture of two di-astereoisomers (trans and cis) in high yields, while longer reaction time and higher temperature were needed in the case of non-cyclic nitrones. Under similar conditions the reaction of quinoline N-oxide (14) with 1 did not give the expected adducts and a ring-opening product was obtained.
基金Project supported by the National Natural Science Foundation of China.
文摘A convenient and direct per(poly)fluoroalkylmethyl-introducing cyclopropanation reaction was described. In the presence of CrCl3/Fe, per(poly)fluoroalkyl iodides reacted with diethyl allylmalonate and its analogs to give per(poly)fluoroalkylmethyl-substituted electrophilic cyclopropane derivatives in high yields. This reaction was considered to proceed by two steps: radical addition followed by cyclopropanation.
基金Project supported by the National Natural Science Foundation of China （No. 20172065）.
文摘The reaction of 3-（1-hydropolyfluoroalkenyl）-1-oxo-2,4,1-benzoxazines 1 with some dinucleophiles was investigated. 7-Fluoroalkyl-2,3-dihydro- 1,4-diazepine[ 1,2-d]quinazolin- 11-ones 2, 2-fluoroalkylisoxazolo[3,2-b]quinazolin-9-ones 3 and 2-fluoroalkylbenzoimidazoles 4 were obtained from the reaction of 1 with 1,2-diaminoethane, hydroxylamine hydrochloride and 1,2-diaminobenzene respectively.
基金Project financially supported by the National Natural Science Foundation of China(No:29632003)
文摘Initiated by CrCl3/Fe redox couple, per(poly)fluoroalkyl iodides added to methyl a-acetylamino acrylate, giving B-per(poly)fluoroalkyl a-amino acid derivatives in good yields.
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.
