新型多氟芳烃-并H-吡唑并[5,1-α]异喹啉衍生物的合成

以2-取代乙炔基取代苯甲醛腙和多氟芳烃为原料,经一锅法串联反应合成了7种新型的多氟芳烃-并H-吡唑并[5,1-α]异喹啉衍生物,其结构经1HNMR,19F NMR和HR-FSI-MS表征.     

新型多氟芳烃-并H-吡唑并[5,1-a]异喹啉衍生物的合成

以2-取代乙炔基取代苯甲醛腙和多氟芳烃为原料,经一锅法串联反应合成了7种新型的多氟芳烃-并H-吡唑并[5,1-a]异喹啉衍生物,其结构经1H NMR,19F NMR和HR-ESI-MS表征。     

简便的"一锅法"合成氟代芳烃

本文采用改进的Schiemann反应, 合成了一些用Schiemann反应不易制得的氟代芳烃。本方法中, 芳烃氟硼酸重氮盐水溶液可不经分离, 室温下"一锅法"反应, 简便合成了对氟硝基苯、对氟苯乙酮, 氟代苯甲酸等, 分离产率为25-62%。     

由芳基卤化物、芳基硼酸和芳烃一锅法合成单氟甲氧基芳烃

介绍了一锅法实现芳烃及其衍生物的单氟甲氧基化反应的过程.利用一系列催化反应,使得芳基卤化物、芳基硼酸和芳烃分别原位生成酚,再利用一氟碘甲烷作为单氟甲基化试剂,合成单氟甲氧基芳烃,反应收率为51%~93%,在传统的苯酚直接亲电单氟甲基化反应的基础上进一步扩大了该方法的应用范围,该方法也适用于一些结构复杂的化合物和一些药物分子结构的后修饰.     

镍催化下一溴二氟甲烷对(杂)芳基溴代物的二氟甲基化反应（英文）

二氟甲基取代的(杂)芳烃化合物由于二氟甲基的独特性质越来越受到了化学家和药物学家的广泛关注.在过去的几年中,大量合成该类化合物的方法不断被发展,但这些方法中大多使用了价格昂贵的需要多步合成的二氟甲基化试剂,从而制约了其广泛应用.因此,发展以廉价易得的二氟甲基化试剂为氟源制备二氟甲基(杂)芳烃化合物的方法是十分必要的.以廉价易得的溴二氟甲烷(BrCF2H)为二氟甲基化试剂,发展了镍催化下(杂)芳基溴代物与Br CF2H的偶联反应.该反应高效温和,底物普适性好,官能团兼容性优秀,并且可以克量级合成,为合成二氟甲基(杂)芳烃化合物提供了一种高效简洁、廉价的方法.初步机理研究表明,该反应经历了一种镍催化的还原偶联历程.     

可见光驱使铜盐催化芳香烃二氟烷基化反应

以CuI为铜源, 通过原位形成光催化剂的途径, 实现了室温下可见光驱使铜催化溴二氟乙酸乙酯、溴二氟酰胺等对芳烃及杂芳烃的二氟烷基化反应. 该反应条件温和、原料廉价易得、底物适用范围广、产率较高, 为合成二氟烷基(杂)芳烃化合物提供了一种方法. 机理研究表明, 该反应可能经历了单电子转移的自由基反应历程.     

硝基多环芳烃还原－七氟丁酸酐衍生物在不同极性色谱柱上保留特性的研究

本文对硝基多环芳烃还原－七氟丁酸酐衍生物的色谱保留行为进行了研究。分别在ＳＥ－５４，ＳＥ－５２和ＨＰ－１７色谱柱上测定了十七种硝基多环芳烃还原产物氨基多环芳烃－七氟丁酸酐衍生物的色谱保留指数。提出了适合于ＥＣＤ保留指数测定的七氟丁酸酐衍生物保留指数系统，该保留指数与Ｌｅｅ指数间有良好的相关性。探讨了初始温度对保留指数的影响。有关结果可用于硝基多环芳烃或氨基多环芳烃的分析。     

硝基多环芳烃还原－七氟丁酸酐衍生物在不同极性色谱柱上保留特性的研究

 本文对硝基多环芳烃还原－七氟丁酸酐衍生物的色谱保留行为进行了研究。分别在ＳＥ－５４，ＳＥ－５２和ＨＰ－１７色谱柱上测定了十七种硝基多环芳烃还原产物氨基多环芳烃－七氟丁酸酐衍生物的色谱保留指数。提出了适合于ＥＣＤ保留指数测定的七氟丁酸酐衍生物保留指数系统，该保留指数与Ｌｅｅ指数间有良好的相关性。探讨了初始温度对保留指数的影响。有关结果可用于硝基多环芳烃或氨基多环芳烃的分析。     

芳烃三氟乙基醚衍生物的制备

芳烃三氟乙基醚;制备;亲核取代;三氟乙醇     

钯催化下Et3SiH对多氟芳烃邻位C—F键选择性活化:一种高效合成部分氟化芳烃的方法

部分氟化的芳烃类化合物在生命和材料科学中具有重要的应用.然而,商业化的含氟芳烃化合物却十分有限,其合成也存在困难.因此,发展合成部分氟化芳烃类化合物的方法十分重要.以廉价易得的多氟芳烃化合物为原料,对其C—F键进行选择性活化还原是一种有效合成部分氟化芳烃类化合物的方法.近期中国科学院上海有机化学研究所张新刚课题组发展出一种以E3SiH为氢源,钯催化下     

Transition-metal-free synthesis of alternating thiophene-perfluoroarene copolymers

The fluoride-activated coupling between silyl-functionalized thiophene monomers and perfluoroarenes leads to moderately high-molecular-weight alternating copolymers in excellent yields and high chemical purity. The method bypasses transition-metal catalysis and the associated need for perfluoroarenes carrying additional functional "handles". Small-molecule model studies provide insight into the relative reactivities of functional groups in this synthetic pathway.     

Formation of perfluorinated polyphenylenes by multiple pentafluorophenylation using C6F5Si(CH3)3

Pentafluorophenylation of perfluoroarenes with C₆F₅Si(CH₃)₃ was investigated by using NMR and MALDI-TOF-MS techniques. Successive multiple pentafluorophenylation easily occurred not only on the para-position but also on the ortho-positions to provide perfluorinated p-phenylene and m-phenylene compounds. The perfluoroarenes having electron-withdrawing substituents provided oligo- to poly-(phenylene)s depending on the added amounts of C₆F₅Si(CH₃)₃, while the perfluoroarenes having electron-donor substituents gave H(C₆F₄)_nF polymers produced from C₆F₅H, which was the decomposed product of C₆F₅Si(CH₃)₃.     

CF Activation in Perfluorinated Arenes with Isonitriles under UV‐Light Irradiation

Due to the great value of fluorinated arenes in agrochemistry, medicinal chemistry and materials science, development of methods for preparation of fluorinated arenes is of high importance. They can be either accessed by arene fluorination or by partial arene defluorination. However, the carbon?fluorine bond belongs to the strongest σ‐bonds, which renders C?F activation highly challenging. Here it is shown that aryl and alkyl isonitriles efficiently activate the strong C?F bond in perfluoroarenes by simple UV irradiation under mild conditions. Reactions proceed by formal direct insertion of the isonitrile into the C?F bond without any transition metal. Activation occurs at arene C?F bonds whereas aliphatic C?F bonds remain unreacted. For selected perfluoroarenes C?F activation occurs with high regioselectivity and resulting imidoyl fluorides are transformed into other valuable compounds. Theoretical studies give insights into the reaction mechanism.     

Pd-catalyzed olefination of perfluoroarenes with allyl esters

An efficient Pd(II)-catalyzed direct olefination of perfluoroarenes with allyl esters is demonstrated. Under the typical conditions, the coupling reaction of fluorinated-arenes with allylic esters proceeded via a β-H elimination rather than a β-OAc elimination to give the corresponding γ-substituted allylic esters.     

Benzodichalcogenophenes with perfluoroarene termini

Benzodichalcogenophenes are functionalized at their termini via SN Ar reactions of their bismetalates with perfluoroarenes. The identities of X, Y, and W are varied to study the effects on LUMO energy levels and crystallization motif. X-ray crystallography reveals that nearly all new derivatives crystallize with coplanar ring systems within slipped 1D or 2D pi-stacks.     

Regioselective C–S bond formation accomplished by copper-catalyzed regioselective C–F substitution of perfluoroarenes with aryl thioacetates or benzyl thioacetate

Practical and straightforward method for regioselective C–S bond formation accomplished by copper-catalyzed regioselective C–F substitution of electron-deficient perfluoroarenes with aryl thioacetates or benzyl thioacetate has been developed. Because of its high reaction efficiency, good chemoselectivity and regioselectivity, and excellent functional-group compatibility, this protocol provides a useful and operationally simple access to polyfluoroaryl thioethers used for drugs and material chemistry.     

One‐pot synthesis of polyfluoroterphenyls via palladium‐catalyzed Suzuki–Miyaura coupling of chlorobromobenzene and CH bond functionalization of perfluoroarenes

An efficient tandem route for the synthesis of polyfluoroterphenyl derivatives has been developed. The target compounds were obtained in moderate to good yields by a Pd(OAc)₂‐catalyzed three‐component coupling reaction involving palladium‐catalyzed direct C? H activation of perfluoroarenes. This in turn will set the stage for a wide application of this useful reaction for the synthesis of fluorinated liquid crystal compounds containing the privileged polyfluoroterphenyl structure. Copyright © 2014 John Wiley & Sons, Ltd.     

Efficient, high-yield route to long, functionalized p-phenylene oligomers containing perfluorinated segments, and their cyclodimerizations by zirconocene coupling

Linear oligophenylene diynes containing 6, 9, and 12 phenylene rings were synthesized in high yields using the nucleophilic aromatic substitution (S(N)Ar) of perfluoroarenes by aryllithium reagents as the key carbon-carbon bond-forming reaction. This reaction was demonstrated to proceed readily at low temperatures with sterically hindered substrates and in the presence of base-sensitive silylalkynyl groups. Diynes synthesized by this methodology were readily zirconocene-coupled into large dimeric macrocycles using the zirconocene reagent Cp(2)Zr(py)(Me(3)SiC triple bond CSiMe(3)).     

Competition of Nucleophilic Aromatic Substitution, σ‐Bond Metathesis,and syn Hydrometalation in Titanium(III)‐Catalyzed Hydrodefluorination of Arenes

Several functionalized and non‐functionalized perfluoroarenes were catalytically transformed into their para‐hydrodefluorinated products by using catalytic amounts of titanocene difluoride and stoichiometric amounts diphenylsilane. Turnover numbers of up to 93 were observed. Solution density functional theory calculations at the M06‐2X/TZ(PCM)//M06‐2X/TZ(PCM) level of theory provided insight into the mechanism of Ti^III‐catalyzed aromatic hydrodefluorination. Two different substrate approaches, with a Ti–F interaction (pathway A) and without a Ti–F interaction (pathway B), are possible. Pathway A leads to a σ‐bond metathesis transition state, whereas pathway B proceeds by means of a two‐step mechanism through a syn‐hydrometalation intermediate or through a Meisenheimer intermediate. Both pathways are competitive over a broad range of substrates.     

Copper-catalyzed direct C-H oxidative trifluoromethylation of heteroarenes

This article describes the copper-catalyzed oxidative trifluoromethylation of heteroarenes and highly electron-deficient arenes with CF(3)SiMe(3) through direct C-H activation. In the presence of catalyst Cu(OAc)(2), ligand 1,10-phenanthroline and cobases tert-BuONa/NaOAc, oxidative trifluoromethylation of 1,3,4-oxadiazoles with CF(3)SiMe(3) proceeded smoothly using either air or di-tert-butyl peroxide as an oxidant to give the corresponding trifluoromethylated 1,3,4-oxadiazoles in high yields. Di-tert-butyl peroxide was chosen as the suitable oxidant for oxidative trifluoromethylation of 1,3-azoles and perfluoroarenes. Cu(OH)(2) and Ag(2)CO(3) were the best catalyst and oxidant for direct oxidative trifluoromethyaltion of indoles. The optimum reaction conditions enable oxidative trifluoromethylation of a range of heteroarenes that bear numerous functional groups. The prepared trifluoromethylated heteroarenes are of importance in the areas of pharmaceuticals and agrochemicals. The preliminary mechanistic studies of these oxidative trifluoromethylations are also reported.