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Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent ·CF_(2)H, CF_(2)H^(+), and :CF_(2) reactivities
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作者 Yuan-Qing Gu Hong-Xin Long +2 位作者 Dan-Dan Zhang Mei-Feng Ruan Guo-Kai Liu 《Science China Chemistry》 SCIE EI CAS CSCD 2024年第3期953-962,共10页
Development of practical and versatile electrophilic difluoromethylating reagent is still a grand challenge so far due to its inherent instability or low reactivity.Herein,we report the design and synthesis of difluor... Development of practical and versatile electrophilic difluoromethylating reagent is still a grand challenge so far due to its inherent instability or low reactivity.Herein,we report the design and synthesis of difluoromethyl phenoxathiinium tetrafluoroborate(PT-CF_(2)H^(+)BF_(4)^(-)) as a novel difluoromethylating reagent,which proves to be a bench-stable,general,powerful and versatile reagent with divergent·CF_(2)H,CF_(2)H^(+),and:CF_(2) reactivities.Making use of this reagent,we demonstrated a vast array of difluoromethyl radical transfer reactions via diverse pathways involving photocatalyst-free visible-light induction,visible-light photoredox catalysis and visible-light mediation single electron transfer of EDA complex.Moreover,the green and highly effective CF_(2)H^(+) and:CF_(2) transfer reactions were also readily accomplished. 展开更多
关键词 difluoromethyl phenoxathiinium salt versatile difluoromethylating reagent difluoromethyl radical difluoromthyl cation DIFLUOROCARBENE
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Ligand-Controlled Copper-Catalyzed Highly Regioselective Difluoromethylation of Allylic Chlorides/Bromides and Propargyl Bromides 被引量:4
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作者 Yang Gu Changhui Lu +1 位作者 Yucheng Gu Qilong Shen 《Chinese Journal of Chemistry》 SCIE CAS CSCD 2018年第1期55-58,共4页
Highly regiodivergent copper-catalyzed allylic/propargylic difluoromethylation reactions by employing different ligands are described. When 5,6-dimethyl-1,10-phenanthroline was used as the ligand, exclusively α-diflu... Highly regiodivergent copper-catalyzed allylic/propargylic difluoromethylation reactions by employing different ligands are described. When 5,6-dimethyl-1,10-phenanthroline was used as the ligand, exclusively α-difluoromethylated products were obtained, while γ-selective difluoromethylated products were generated when N-heterocyclic carbene-SIPr was used as the ligand. Likewise, high α- vs. γ-selectivities were achieved in the presence of similar copper catalysts for the reactions of propargyl bromides. Moreover, a copper-catalyzed asymmetric allylic difluoromethylation reaction with moderate to good enantioselectivity by the use of chiral ligands was developed. 展开更多
关键词 fluorine difluoromethyl copper asymmetric allylic substitution
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Pentacoordinate Phosphoranes as Versatile Reagents in Fluoroalkylation Reactions
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作者 Huanhuan Song Weihao Li +7 位作者 Xiaoying Wang Kaiteng Wang Jingwen Li Shuai Liu Pin Gao Xin-Hua Duan Jinbo Hu Mingyou Hu 《CCS Chemistry》 CSCD 2024年第1期165-176,共12页
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
关键词 pentacoordinate phosphorane difluoromethyl radical DIFLUOROCARBENE difluoromethylATION FLUOROALKYLATION
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Selective O-difluoromethylation of 1,3-diones using S-(difluoromethyl) sulfonium salt 被引量:2
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作者 Guo-Kai Liu Xin Li +4 位作者 Wen-Bing Qin Wei-Feng Lin Li-Ting Lin Jia-Yi Chen Jian-Jian Liu 《Chinese Chemical Letters》 SCIE CAS CSCD 2019年第8期1515-1518,共4页
A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described.And a broad range of difluoromthyl enol ethers... A facile and highly efficient approach for selective O-difluoromethylation of 1,3-diones by recently developed bench-stable S-(difluoromethyl)sulfonium salt was described.And a broad range of difluoromthyl enol ethers were readily accessed in good to excellent yields under mild reaction conditions.Mechanistic studies revealed that the O-difluoromethylation reaction proceeds mainly via a difluorocarbene pathway. 展开更多
关键词 DIFLUOROCARBENE difluoromethyl ENOL ethers 1 3-Diones O-difluoromethylation S-(Difluoromethy)sulfonium salt
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二氟甲基在生理活性物质中的应用及二氟甲基化反应研究进展 被引量:4
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作者 陈越 孟章富 毕作伟 《有机氟工业》 CAS 2015年第4期20-26,共7页
介绍了含二氟甲基的化合物在新型医药、农药等生理活性物质创制中的应用,并介绍了近年来向芳烃及杂环底物中引入二氟甲基的研究进展。
关键词 二氟甲基 二氟甲基化 含氟医药 含氟农药
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Mechanochemical Difluoromethylations of Alcohols
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作者 Pit van Bonn Jinbo Ke +3 位作者 Christopher Weike Jas SWard Kari Rissanen Carsten Bolm 《CCS Chemistry》 CSCD 2023年第8期1737-1744,共8页
Difluoromethyl ethers are formed through mechanochemical reactions of alcohols with difluorocarbene in a mixer mill.The protocol could be applied to primary,secondary,and tertiary alcohols,yielding the corresponding p... Difluoromethyl ethers are formed through mechanochemical reactions of alcohols with difluorocarbene in a mixer mill.The protocol could be applied to primary,secondary,and tertiary alcohols,yielding the corresponding products in excellent yields(up to 99%)after 1 h reaction time at room temperature.The transformations proceeded under solvent-free reaction conditions,followed by product purification by filtration,which drastically reduced the amount of waste generated during the process. 展开更多
关键词 MECHANOCHEMISTRY ball milling solventfree reaction DIFLUOROCARBENE difluoromethyl ether
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An efficient three-component domino synthesis of difluoromethyl-containing 1,4-dihydropyridines under solvent and catalyst free conditions 被引量:1
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作者 LI Hui YU JinLong +4 位作者 CAO Song SHEN Li WU MingXi CHENG JianHang QIAN XuHong 《Science China Chemistry》 SCIE EI CAS 2010年第7期1509-1513,共5页
The difluoromethyl-containing Hantzsch 1,4-dihydropyridines were synthesized in good yields by a one-pot cyclocondensation of ethyl difluoroacetoacetate (EDFAA),a variety of aromatic aldehydes and ammonium acetate und... The difluoromethyl-containing Hantzsch 1,4-dihydropyridines were synthesized in good yields by a one-pot cyclocondensation of ethyl difluoroacetoacetate (EDFAA),a variety of aromatic aldehydes and ammonium acetate under solvent and catalyst free conditions.The comparison of reaction conditions and products was made among the different 1,3-carbonyl substrates (ethyl acetoacetate,ethyl difluoroacetoacetate and ethyl trifluoroacetoacetate) for the Hantzsch reaction. 展开更多
关键词 THREE-COMPONENT difluoromethyl 1 4-dihydropyridines ethyl difluoroacetoacetate
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可见光催化下N-芳基甲基丙烯酰胺的二氟甲基化/环化反应研究
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作者 罗蛟 黄丹凤 +1 位作者 王克虎 胡雨来 《合成化学》 CAS 2023年第4期276-282,共7页
研究了利用二氟乙酸酐作为二氟甲基自由基源,在可见光催化下的N-芳基甲基丙烯酰胺的二氟甲基化/环化反应,合成了一系列3-甲基-3-二氟乙基吲哚酮类化合物。结果表明:该方法操作简单,产率较高,可达91%,底物适用范围广。
关键词 二氟甲基 光催化 N-芳基甲基丙烯酰胺 二氟乙酸酐 甲基化/环化反应
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二氟甲基的应用和二氟乙酸酯的合成研究 被引量:4
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作者 肖恒侨 韩国庆 +2 位作者 徐卫国 项文勤 陈明炎 《有机氟工业》 CAS 2013年第3期13-17,共5页
介绍了二氟甲基的应用,并根据起始原料的不同,对二氟甲基的的重要合成砌块二氟乙酸酯的合成工艺进行优缺点分析和探讨。
关键词 二氟甲基 二氟乙酸酯 合成 应用
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3-氨基-6-二氟甲基喹啉的合成
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作者 卢润轩 赵丽芳 +2 位作者 张玲 徐卫良 徐炜政 《精细化工中间体》 CAS 2023年第1期49-53,共5页
对重要中间体3-氨基-6-二氟甲基喹啉的合成工艺进行了研究,首次以6-喹啉甲酸为起始原料,经过酰化、二氟甲基化、溴化、钯催化偶联、氨基脱保护等反应合成了3-氨基-6-二氟甲基喹啉,总收率31.4%。其结构经^(1)H NMR、^(13)C NMR和LC-MS确证。
关键词 3-氨基-6-二氟甲基喹啉 二氟甲基 合成
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Facile synthesis of α-difluoromethyl α-propargylamines from CF_2H-substituted N-tert-butanesulfinyl ketimines 被引量:1
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作者 Hui Chen Wei Yu +2 位作者 Xin Hua Guo Wei Dong Meng Yan Gen Huang 《Chinese Chemical Letters》 SCIE CAS CSCD 2012年第3期277-280,共4页
Stereoselective approach for preparation ofα-difluoromethylα-propargylamines has been developed.1,2-Addition of lithium acetylides to diverse chiral difluoromethylated(S)-N-tert-butanesulfinyl ketimines by using T... Stereoselective approach for preparation ofα-difluoromethylα-propargylamines has been developed.1,2-Addition of lithium acetylides to diverse chiral difluoromethylated(S)-N-tert-butanesulfinyl ketimines by using Ti(O^iPr)_4 as catalyst and THF as solvent afforded N-tert-butanesulfinamides in good to excellent yields(51-93%) and good diastereoselectivities(dr.85:15 to 93:7).The N-tert -butanesulfinyl group can be readily cleaved under mild acidic condition(4 mol/L HCl in dioxane) to provide the correspondingα-difiuoromethylα-propargylamine in excellent yields(90-95%). 展开更多
关键词 Diasteroselectivity difluoromethyl PROPARGYLAMINE 1 2-Addition Sulfinamides
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Deconstrutive Difunctionalizations of Cyclic Ethers Enabled by Difluorocarbene to Access Difluoromethyl Ethers 被引量:1
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作者 Heyun Sheng Jianke Su +1 位作者 Xue Li Qiuling Song 《CCS Chemistry》 CAS 2022年第12期3820-3831,共12页
An unprecedented difluorocarbene-mediated C-O bond cleavage of cyclic ethers for the construction of difluoromethyl ethers is herein disclosed.This protocol is distinguished by its mild conditions,high efficiency,and ... An unprecedented difluorocarbene-mediated C-O bond cleavage of cyclic ethers for the construction of difluoromethyl ethers is herein disclosed.This protocol is distinguished by its mild conditions,high efficiency,and wide substrate scope,which can tolerate both sensitive functional groups such as the hydroxyl group,olefin and C-C triple bonds,as well as complex molecules.It thus demonstrates excellent chemoselectivities and great potential for late-stage modification of pharmaceutical compounds and natural products.It is worth noting that this method not only introduces fluorine atoms into the final molecules,but it can also effectively form an ester or ether linkage. 展开更多
关键词 DIFLUOROCARBENE C-O bond cleavage cyclic ethers difluoromethyl ethers
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生物电子等排体二氟甲基在药物化学中的应用及其化学合成方法进展 被引量:2
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作者 张寅生 《药学学报》 CAS CSCD 北大核心 2021年第8期2182-2196,共15页
生物电子等排是药物结构优化中最常见的一种策略,随着药物化学和有机化学的发展,越来越多的经典的和非经典的生物电子等排体被运用到新药的设计中,近几年来,含氟基团作为生物电子等排体越来越受到药物化学家们的重视,本文扼要地综述二... 生物电子等排是药物结构优化中最常见的一种策略,随着药物化学和有机化学的发展,越来越多的经典的和非经典的生物电子等排体被运用到新药的设计中,近几年来,含氟基团作为生物电子等排体越来越受到药物化学家们的重视,本文扼要地综述二氟甲基(CF_(2)H)的理化性质、化学制备方法及其在药物设计中的应用,旨在为新药研究人员提供参考。 展开更多
关键词 生物电子等排体 二氟甲基 理化性质 药物设计 合成方法
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Full-Spectrum Fluoromethyl Sulfonation via Modularized Multicomponent Coupling
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作者 Kejie Li Ming Wang Xuefeng Jiang 《CCS Chemistry》 CAS 2022年第5期1526-1534,共9页
Modular free-assembly construction of mono-,di-,and tri-fluoromethyl sulfones was comprehensively achieved by a combination of halides,a sulfur dioxide surrogate,and halofluorocarbons.The industrial raw material thiou... Modular free-assembly construction of mono-,di-,and tri-fluoromethyl sulfones was comprehensively achieved by a combination of halides,a sulfur dioxide surrogate,and halofluorocarbons.The industrial raw material thiourea dioxide served as the sulfur dioxide source,combined with readily available fluorocarbon sources such as 2-bromo-2-fluoroacetate and chlorodifluoromethane(ClCF_(2)H,Freon)employed as fluoromethyl reagents.Notably,four methyl sulfone-containing pharmaceuticals were modified into three types of fluoromethyl sulfones,displaying their great potential for drug discovery via the current strategy.Mechanistic studies further demonstrated that C-F…H-N interactions between thiourea dioxide and halofluorocarbons play a key role in stabilizing monofluoromethyl electrophiles and difluorocarbene species. 展开更多
关键词 SULFONE trifluoromethyl sulfone difluoromethyl sulfone monofluoromethyl sulfone thiourea dioxide
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Palladium Difluorocarbene Involved Catalytic Coupling with Terminal Alkynes 被引量:1
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作者 Xue-Ying Zhang Xia-Ping Fu +1 位作者 Shu Zhang Xingang Zhang 《CCS Chemistry》 CAS 2020年第5期293-304,共12页
Difluoromethylated alkynes are a versatile synthon for the diversity-oriented synthesis of difluoromethyl compounds that are of great interest in life and materials sciences.However,the catalytic cross-coupling for th... Difluoromethylated alkynes are a versatile synthon for the diversity-oriented synthesis of difluoromethyl compounds that are of great interest in life and materials sciences.However,the catalytic cross-coupling for the synthesis of difluoromethylated alkynes remains challenging,despite impressive achievements made in the cross-coupling reactions for alkynes,including the Sonogashira reaction.Here,we report a palladium difluorocarbene involvement in catalytic coupling with terminal alkynes,representing a new mode of conjugation reaction,which circumvents the radical pathway usually encountered during the coupling of alkynes with fluoroalkyl electrophiles.The reaction uses inexpensive and abundant industrial raw material chlorodifluoromethane(ClCF_(2)H)as the difluorocarbene precursor,and features cost-effectiveness,excellent functional group tolerance,and broad substrate scope,including synthesis of drug-like complex molecules.Our mechanistic studies showed a unique catalytic pathway of this process,in which additive hydroquinone plays a pivotal role in promoting the reaction. 展开更多
关键词 ALKYNES CROSS-COUPLING DIFLUOROCARBENE difluoromethyl PALLADIUM
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新型螺[氧化吲哚-3,3'-吡唑]-5'-二氟甲基-4'-甲酸酯类化合物的合成 被引量:1
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作者 韩文勇 赵佳 +1 位作者 崔宝东 陈永正 《合成化学》 CAS CSCD 北大核心 2018年第5期328-331,342,共5页
以原位生成的二氟甲基重氮甲烷(CF_2HCHN_2)与靛红衍生的3-烯基氧化吲哚为原料,通过[3+2]环加成反应和1,3-H迁移过程,合成了3种结构新型的螺[氧化吲哚-3,3'-吡唑]-5'-二氟甲基-4'-甲酸酯类化合物,收率41~68%,dr 91∶9~99∶1... 以原位生成的二氟甲基重氮甲烷(CF_2HCHN_2)与靛红衍生的3-烯基氧化吲哚为原料,通过[3+2]环加成反应和1,3-H迁移过程,合成了3种结构新型的螺[氧化吲哚-3,3'-吡唑]-5'-二氟甲基-4'-甲酸酯类化合物,收率41~68%,dr 91∶9~99∶1,其结构经~1H NMR,^(13)C NMR,^(19)F NMR和HR-MS(ESI-TOF)表征。并通过单晶X-射线单晶衍射确定其相对构型。 展开更多
关键词 二氟甲基 3 3’-螺环氧化吲哚 [3+2]环加成 1 3-H迁移 合成 相对构型
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(Z)-(2-溴-3,3-二氟丙-1-烯-1-基)苯衍生化反应研究
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作者 谢波 高恋 +3 位作者 吴思莹 白亚超 胡志豪 陈定奔 《化学试剂》 CAS 北大核心 2021年第10期1448-1451,共4页
研究了新的二氟甲基砌块化合物的衍生化反应。首先以α-溴代肉桂醛和二乙胺基三氟化硫为原料合成标题化合物砌块,接着将该砌块在DMF溶剂中,以碳酸铯作碱,并将环境温度控制在80℃下反应过夜得到(3,3-二氟丙-1-炔-1-基)苯,接着与系列含氮... 研究了新的二氟甲基砌块化合物的衍生化反应。首先以α-溴代肉桂醛和二乙胺基三氟化硫为原料合成标题化合物砌块,接着将该砌块在DMF溶剂中,以碳酸铯作碱,并将环境温度控制在80℃下反应过夜得到(3,3-二氟丙-1-炔-1-基)苯,接着与系列含氮杂环发生反应合成4个(Z)-1-(3,3-二氟-1-苯基丙-1-烯-1-基)-1H-唑化合物,产率为28.2%~62.1%。同时合成了2个含有二氟甲基的中间体和4个拓展产物,其结构经^(1)HNMR、^(13)CNMR、^(19)FNMR、HR-MS进行了表征。 展开更多
关键词 (Z)-(2-溴-3 3-二氟丙-1-烯-1-基)苯 二氟甲基 衍生化 结构表征
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2-二氟甲氧(硫)基吡啶-5-硼酸频哪醇酯类化合物的合成
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作者 吴清梅 张秋艳 +1 位作者 黄朋越 周志旭 《化学研究与应用》 CAS CSCD 北大核心 2021年第4期731-734,共4页
以吡啶类化合物作为起始原料,先经二氟甲基化反应在羟基或巯基上引入二氟甲基基团,再用铱催化剂活化吡啶环的C-H并直接引入硼酸频哪醇酯基团,得到目标化合物,其产物结构经^(1)H NMR、^(13)C NMR、MS和元素分析确证。该方法具有合成路线... 以吡啶类化合物作为起始原料,先经二氟甲基化反应在羟基或巯基上引入二氟甲基基团,再用铱催化剂活化吡啶环的C-H并直接引入硼酸频哪醇酯基团,得到目标化合物,其产物结构经^(1)H NMR、^(13)C NMR、MS和元素分析确证。该方法具有合成路线较短、反应条件温和、原料廉价易得以及产率较高等优点。 展开更多
关键词 二氟甲基 硼酸酯化合物 铱催化剂 合成
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3,4-二取代-3-(二氟甲基)吡唑类化合物的构建 被引量:8
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作者 曾俊良 许志红 马军安 《有机化学》 SCIE CAS CSCD 北大核心 2020年第5期1105-1116,共12页
二氟甲基在活性分子中可以起到氢键供体、生物电子等排体、亲脂性调节等作用,在药物和农药分子的设计中被广泛使用.3,4-二取代-3-(二氟甲基)吡唑骨架的发现及应用是该领域的一个突出代表,研究表明含有这类骨架的分子能够抑制琥珀酸脱氢... 二氟甲基在活性分子中可以起到氢键供体、生物电子等排体、亲脂性调节等作用,在药物和农药分子的设计中被广泛使用.3,4-二取代-3-(二氟甲基)吡唑骨架的发现及应用是该领域的一个突出代表,研究表明含有这类骨架的分子能够抑制琥珀酸脱氢酶(SDHIs),具有作为杀菌剂的潜力,目前市场上已有近十种农药分子含有3,4-二取代-3-(二氟甲基)吡唑结构单元,年销售额高达十几亿美元.按照所用含氟砌块的不同种类,对近二十年来3,4-二取代-3-(二氟甲基)吡唑类化合物的合成方法进行总结和展望. 展开更多
关键词 3 4-二取代-3-(二氟甲基)吡唑 二氟甲基杂环化合物 杀菌剂 合成
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氧化锌促进的醛与[Ph3P+CF2H·Br-]的Wittig偕二氟烯基化反应(英文) 被引量:5
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作者 于蛟 林锦鸿 肖吉昌 《有机化学》 SCIE CAS CSCD 北大核心 2019年第1期265-269,共5页
以氧化锌为碱实现了醛与二氟甲基鏻盐[Ph3P+CF2H·Br-]的Wittig偕二氟烯基化反应.虽然鏻盐中二氟甲基上的氢原子具有一定酸性,但是碱不一定就会与其发生中和反应而使鏻盐转化为叶立德.碱也有可能进攻磷原子而产生具有亲核性的二氟... 以氧化锌为碱实现了醛与二氟甲基鏻盐[Ph3P+CF2H·Br-]的Wittig偕二氟烯基化反应.虽然鏻盐中二氟甲基上的氢原子具有一定酸性,但是碱不一定就会与其发生中和反应而使鏻盐转化为叶立德.碱也有可能进攻磷原子而产生具有亲核性的二氟甲基物种,从而发生亲核二氟甲基化.以氧化锌为碱可抑制二氟甲基化,有利于Wittig反应;此外,氧化锌及其产生的锌盐都可经简单过滤而除去,方便产物纯化. 展开更多
关键词 WITTIG 偕二氟烯基化 二氟甲基鏻盐 氧化锌
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