- Metalated Porous Phenanthroline-Based Polymers as Efficient Heterogeneous Catalysts for Regioselective C?H Activation of Heteroarenes
-
Direct C?H bond activation of heterocycles as a step-economical and environmentally friendly approach to build the heterobiaryls motifs is highly attractive, but it still has a challenge to design and prepare a cheap and regioselective heterogeneous catal
- Tang, Yongquan,Dai, Zhifeng,Wang, Sai,Chen, Fang,Meng, Xiangju,Xiao, Feng-Shou
-
p. 2469 - 2474
(2021/08/06)
-
- Infrared Irradiation-Assisted Solvent-Free Pd-Catalyzed (Hetero)aryl-aryl Coupling via C?H Bond Activation
-
The increasing attention towards environmentally friendly synthetic protocols has boosted studies directed to the development of green and sustainable methods for direct C?H bond arylation of (hetero)arenes. In this context, here the infrared (IR) irradia
- Albano, Gianluigi,Decandia, Gianfranco,Capozzi, Maria Annunziata M.,Zappimbulso, Nicola,Punzi, Angela,Farinola, Gianluca M.
-
p. 3391 - 3401
(2021/07/28)
-
- Synthesis of 2-Substituted Benzothio(seleno)phenes and Indoles via Ag-Catalyzed Cyclization/Demethylation of 2-Alkynylthio(seleno)anisoles and 2-Alkynyldimethylanilines
-
An Ag-catalyzed cyclization/demethylation of 2-alkynylthio(seleno)anisoles and 2-alkynyldimethylanilines is described and applied for the construction of valuable benzothio(seleno)phenes as well as indoles. Various 2-substituted benzothio(seleno)phenes and indoles were obtained in good to excellent yields under mild reaction conditions with low catalyst loading. An application of this new method is also exemplified with a concise synthesis of a bioactive molecule precursor. Furthermore, a conceivable reaction mechanism is proposed with supports from isotope-exchange experiments.
- Cai, Tao,Feng, Chengjie,Shen, Fangqi,Bian, Kejun,Wu, Chunlei,Shen, Runpu,Gao, Yuzhen
-
p. 653 - 656
(2020/12/23)
-
- Nickel-catalyzed and Li-mediated regiospecific C-H arylation of benzothiophenes
-
A nickel-based catalytic system for the regiospecific C2-H arylation of benzothiophene has been established. NiCl2(bpy) is used as a catalyst in combination with LiHMDS as a base in dioxane. The catalytic system is applicable to a variety of functionalized benzothiophenes, as well as other heteroarenes including thiophene, benzodithiophene, benzofuran and selenophene in combination with iodo aryl electrophiles. The role of LiHMDS as a uniquely potent base and a postulated mechanism are discussed. The applicability of this system is finally demonstrated for the synthesis of an intermediate of an active pharmaceutical ingredient.
- Canivet, Jér?me,Grousset, Léonie,Hisler, Ga?lle,Mohr, Yorck,Quadrelli, Elsje Alessandra,Roux, Yoann,Wisser, Florian M.
-
p. 3155 - 3161
(2020/06/19)
-
- Transition-Metal-Free Synthesis of Heterobiaryls through 1,2-Migration of Boronate Complex
-
The synthesis of a diverse range of heterobiaryls has been achieved by a transition-metal-free sp2–sp2 cross-coupling strategy using lithiated heterocycle, aryl or heteroaryl boronic ester and an electrophilic halogen source. The construction of heterobiaryls was carried out through electrophilic activation of the aryl–heteroaryl boronate complex, which triggered 1,2-migration from boron to the carbon atom. Subsequent oxidation of the intermediate boronic ester afforded heterobiaryls in good yield. A comprehensive 11B NMR study has been conducted to support the mechanism. The cross coupling between two nucleophilic cross coupling partners without transition metals reveals a reliable manifold to procure heterobiaryls in good yields. Various heterocycles like furan, thiophene, benzofuran, benzothiophene, and indole are well tolerated. Finally, we have successfully demonstrated the gram scale synthesis of the intermediates for an anticancer drug and OLED material using our methodology.
- Paul, Swagata,Das, Kanak Kanti,Manna, Samir,Panda, Santanu
-
supporting information
p. 1922 - 1927
(2020/02/04)
-
- C-H Arylation of Thiophenes with Aryl Bromides by a Parts-per-Million Loading of a Palladium NNC-Pincer Complex
-
A palladium NNC-pincer complex efficiently catalyzed the direct arylation of thiophene derivatives with extremely low palladium loadings of the order of parts per million. Thus, the reaction of various thiophenes with aryl bromides in the presence of 25-100 mol ppm of chlorido[(2-phenyl-κ- C 2)-9-phenyl-1,10-phenanthroline-κ 2- N, N ′]palladium(II) NNC-pincer complex, K 2CO 3, and pivalic acid in N, N -dimethyl acetamide afforded the corresponding 2- or 5-arylated thiophenes in good to excellent yields. A combination of the present C-H arylation and Hiyama coupling with the same NNC-pincer complex provides an efficient synthesis of unsymmetrical 2,5-thiophenes with catalyst loadings at mol ppm levels.
- Purta, Anggi Eka,Ichii, Shun,Tazawa, Aya,Uozumi, Yasuhiro
-
supporting information
p. 1634 - 1638
(2020/08/28)
-
- Decarboxylative Suzuki-Miyaura coupling of (hetero)aromatic carboxylic acids using iodine as the terminal oxidant
-
A novel methodology for the decarboxylative Suzuki-Miyaura-type coupling has been established. This process uses iodine or a bromine source as both the decarboxylation mediator and the terminal oxidant, thus avoiding the need for stoichiometric amounts of transition metal salts previously required. Our new protocol allows for the construction of valuable biaryl architectures through the coupling of (hetero)aromatic carboxylic acids with arylboronic acids. The scope of this decarboxylative Suzuki reaction has been greatly diversified, allowing for previously inaccessible non-ortho-substituted aromatic acids to undergo this transformation. The procedure also benefits from low catalyst loadings and the absence of stoichiometric transition metal additives.
- Quibell, Jacob M.,Duan, Guojian,Perry, Gregory J.P.,Larrosa, Igor
-
supporting information
p. 6445 - 6448
(2019/06/07)
-
- Aerobic, Metal-Free, and Catalytic Dehydrogenative Coupling of Heterocycles: En Route to Hedgehog Signaling Pathway Inhibitors
-
The nitrosonium ion-catalyzed dehydrogenative coupling of heteroarenes under mild reaction conditions is reported. The developed method utilizes ambient molecular oxygen as a terminal oxidant, and only water is produced as byproduct. Dehydrogenative coupl
- Bering, Luis,Paulussen, Felix M.,Antonchick, Andrey P.
-
supporting information
p. 1978 - 1981
(2018/04/16)
-
- Arylation synthesis method for novel five-membered aromatic heterocycle and aromatic-ring five-membered aromatic heterocycle
-
The invention belongs to the technical field of organic synthesis and in particular relates to an arylation synthesis method for a five-membered aromatic heterocycle or an aromatic-ring five-memberedaromatic heterocycle under the participation of an arylhydrazine derivative serving as a novel arylation reagent. The method comprises the steps: adding a raw material and aroyl hydrazine into a reactor, and carrying out a reaction at 60-100 DEG C for 8-24h under the condition that an oxidant and a transition metal catalyst are added; after the reaction is ended, carrying out suction filtration, extracting a filtrate by using ethyl acetate, carrying out drying to obtain a crude product of a target compound, and carrying out column chromatography on silica gel to obtain a pure product of the target compound. The arylation synthesis method for the five-membered aromatic heterocycle or the aromatic-ring five-membered aromatic heterocycle is scientific and reasonable and has the advantages such as simplicity and convenience in operation, relatively high yield and simplicity in amplification and purification.
- -
-
Paragraph 0112-0115; 0228-0231; 0236-0239
(2018/07/07)
-
- Method for synthesizing benzothiophene derivative by catalysis of dihalogenated aromatics by copper
-
The invention discloses a method for synthesizing a benzothiophene derivative by catalysis of dihalogenated aromatics by copper. According to the invention, a catalyst cuprous iodide with a catalysisamount, a ligand 8-hydroxyquinoline, an auxiliary catalyst cesium carbonate and 1-bromine-2-iodobenzene or its derivative, sulfur powder, and phenylacetylene or its derivative are added in a flask andsubjected to a reaction in pure water at certain temperature, after a certain time, vacuum concentration is carried out, and a product is purified through column chromatography. The method has the advantages of novel raw material and simple operation, and can be used for efficiently preparing the benzothiophene derivative. Compared with the prior art, the method has the advantages of mild reaction condition, simple operation, high yield, safety, low cost, and environmental protection.
- -
-
Paragraph 0026; 0053
(2018/08/28)
-
- Method for synthesizing benzothiophene derivatives from dihaloarene under microwave irradiation under catalysis of copper
-
The invention discloses a method for synthesizing benzothiophene derivatives from dihaloarene under microwave irradiation under the catalysis of copper. The method comprises the following steps: adding a catalytic amount of a catalyst copper chloride, a ligand 1,10-phenanthroline (1,10-Phen), a cocatalyst potassium hydroxide, 1-bromo-2-iodobenzene and its derivatives, KSCN (potassium thiocyanate),phenylacetylene and pure water, performing a reaction in a microwave reactor at a certain temperature under a certain power for a certain time, performing reduced pressure concentrating, and performing column chromatography purification on the obtained product. The method disclosed in the invention is a method having novel raw materials, being simple to operate and used for efficiently preparingthe benzothiophene derivatives. Compared with the prior art, the method has an obvious faster reaction speed than convectional heating, and has the advantages of mild reaction conditions, simplicity in operation, high yield, safety, low cost and environmental protection.
- -
-
Paragraph 0030; 0057
(2018/09/08)
-
- Oxidative Cross-Coupling of Boron and Antimony Nucleophiles via Palladium(I)
-
The use of an isolatable, monomeric Pd(I) complex as a catalyst for the oxidative cross-coupling of aryl-antimony and aryl-boron nucleophiles is reported. This reaction tolerates a wide variety of substrates, with >20:1 selectivity for cross-coupled products. This strategy offers a new approach to achieving the selective cross-coupling of nucleophiles.
- Simpson, Quillon,Sinclair, Matthew J. G.,Lupton, David W.,Chaplin, Adrian B.,Hooper, Joel F.
-
supporting information
p. 5537 - 5540
(2018/09/21)
-
- Ag(I)-C-H Activation Enables Near-Room-Temperature Direct α-Arylation of Benzo[ b]thiophenes
-
The first example of near-room-temperature α-arylation of benzo[b]thiophenes is reported. The discovery rests on the observation of a switch in α-/β-regioselectivity at different loadings of Pd2(dba)3·CHCl3 in the coupling between benzo[b]thiophene and 4-iodotoluene. We show that this unprecedented regioselectivity switch is driven by a Ag(I)-mediated C-H activation at the α-C-H position, which becomes the dominant mode of reactivity at low concentrations of Pd. Competition experiments, kinetic studies, KIE, and D/H scrambling experiments have been carried out supporting this mechanism.
- Colletto, Chiara,Panigrahi, Adyasha,Fernández-Casado, Jaime,Larrosa, Igor
-
supporting information
p. 9638 - 9643
(2018/07/21)
-
- Palladium/Copper Dual Catalysis for the Cross-Coupling of Aryl(trialkyl)silanes with Aryl Bromides
-
Whereas aryl(trialkyl)silanes are considered to be ideal organometallic reagents for cross-coupling reactions owing to their stability, low toxicity, solubility, and easy accessibility, they are generally inert under typical cross-coupling conditions. Disclosed herein is a palladium/copper catalytic system that enables the cross-coupling of trimethyl, triethyl, tert-butyldimethyl, and triisopropyl aryl silanes with aryl bromides. This process is applicable to the sequential C?H and C?Si bond arylation of thiophenes and the synthesis of poly(thiophene–fluorene)s.
- Komiyama, Takeshi,Minami, Yasunori,Furuya, Yuki,Hiyama, Tamejiro
-
supporting information
p. 1987 - 1990
(2018/02/10)
-
- Synthesis of 2-substituted benzo[: B] thiophenes via gold(i)-NHC-catalyzed cyclization of 2-alkynyl thioanisoles
-
Benzo[b]thiophene heterocycles are important components of many important small molecule pharmaceuticals and drug candidates as well as organic semiconducting materials. Many methods have been developed for the construction of a benzo[b]thiophene core via cyclization reaction of alkynes. Although few catalytic reactions were disclosed, most methods rely on stoichiometric activation of alkynes. Here we report an efficient method for the synthesis of 2-substituted benzo[b]thiophenes from 2-alkynyl thioanisoles catalyzed by a gold(i)-IPr hydroxide that is applicable to a wide range of substrates with diverse electronic and steric properties. Additionally, we demonstrate experimentally that the acid additive and its conjugate base are essential to catalyst turnover.
- Dillon, Christopher C.,Keophimphone, Bagieng,Sanchez, Melissa,Kaur, Parveen,Muchalski, Hubert
-
p. 9279 - 9284
(2019/01/03)
-
- A tridentate CNO-donor palladium(II) complex as efficient catalyst for direct C―H arylation: Application in preparation of imidazole-based push–pull chromophores
-
A series of imidazolium chlorides for the formation of tridentate CNO-donor palladium(II) complexes featuring N-heterocyclic carbene moieties have been developed from cheap and readily available starting materials with high yields. Their palladium complex
- Li, Hui-Hong,Maitra, Ratnava,Kuo, Ya-Ting,Chen, Jie-Hong,Hu, Ching-Han,Lee, Hon Man
-
-
- Arylation method of thiophene compounds
-
The invention provides an arylation method of thiophene compounds. The thiophene compounds are benzothiophene or thiophene, and the benzothiophene represented by formula (1) or thiophene represented by formula (2) and aryl chloride represented by formula
- -
-
Paragraph 0036; 0037; 0038; 0039; 0040; 0041; 0042-0047
(2017/08/28)
-
- Deprotonative Silylation of Aromatic C-H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride
-
A method for the deprotonative silylation of aromatic C-H bonds has been developed using trifluoromethyltrimethylsilane (CF3SiMe3, Ruppert-Prakash reagent) and a catalytic amount of fluoride. In this reaction, CF3SiMe3 is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-containing analogs of TAC-101, which is a bioactive synthetic retinoid with selective affinity for retinoic acid receptor α (RAR-α) binding. We also report further transformations of the silylated products into useful derivatives.
- Nozawa-Kumada, Kanako,Osawa, Sayuri,Sasaki, Midori,Chataigner, Isabelle,Shigeno, Masanori,Kondo, Yoshinori
-
p. 9487 - 9496
(2017/09/23)
-
- Iridium-Catalyzed Asymmetric Hydrogenation of Benzo[b]thiophene 1,1-Dioxides
-
An efficient iridium-catalyzed asymmetric hydrogenation of substituted benzothiophene 1,1-dioxides is described. The use of iridium complexes with chiral pyridyl phosphinite ligands provides access to highly enantiomerically enriched sulfones with substituents at the 2- and 3-position. Sulfones of this type are of interest as core structures of agrochemicals and pharmaceuticals. Moreover, they can be further reduced to chiral 2,3-dihydrobenzothiophenes.
- Tosatti, Paolo,Pfaltz, Andreas
-
supporting information
p. 4579 - 4582
(2017/04/11)
-
- Synthesis of 2-substituted benzo[b]thiophene via a Pd-catalyzed coupling of 2-iodothiophenol with phenylacetylene
-
A Pd(ii)-catalyzed Sonogashira type cross-coupling reaction between 2-iodothiophenol and phenylacetylene has been developed. A series of 2-substituted benzo[b]thiophenes were obtained in moderate to good yield (up to 87%). The application of this method was demonstrated by the synthesis of 2-(4-(tert-butyl)phenyl)benzo[b]thiophene 1,1-dioxide and (4-methoxyphenyl)(2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)methanone, which exhibit a fluorescence quantum yield of up to 1 and can be used as a cannabinoid receptor ligand, respectively.
- Chen, Jingwen,Xiang, Haifeng,Yang, Li,Zhou, Xiangge
-
p. 7753 - 7757
(2017/02/05)
-
- N-Heterocyclic carbene-Pd(II)-1-methylimidazole complex catalyzed C[sbnd]H bond arylation of (benzo)thiophenes with aryl chlorides
-
NHC-Pd(II)-Im complex showed efficient catalytic activity toward the direct C[sbnd]H bond arylation of (benzo)thiophenes with the challenging aryl chlorides. Under the suitable conditions, all reactions proceeded smoothly to give the desired C[sbnd]H bond
- Yin, Shun-Chao,Zhou, Quan,He, Qian-Wei,Li, Shu-Wan,Qian, Peng-Cheng,Shao, Li-Xiong
-
p. 427 - 431
(2017/01/13)
-
- Palladium-Catalyzed Direct C2-Arylation of Benzo[ b ]thiophenes with Electron-Rich Aryl Halides: Facile Access to Thienoacene Derivatives
-
Direct coupling reaction of benzo[ b ]thiophene and electron-rich aryl bromides was achieved under Pd 2 (dba) 3 /SPhos catalysis in the presence of NaO t -Bu. The reaction system was applied for the installation of 2-(methylthio)phenyl group onto thiophene-fused polyaromatic molecules, demonstrating facile synthesis of precursors for thienoacene derivatives.
- Ichioka, Fumiki,Itai, Yuhei,Nishii, Yuji,Miura, Masahiro
-
p. 2812 - 2816
(2017/09/30)
-
- A benzothiophene compound preparation method and its purification method
-
The invention discloses a preparation method for benzothiophene compounds. The preparation method comprises the following steps: 1-bromine(chlorine)-2-styrene benzene or derivatives thereof are used as a substrate; a vulcanizer is added into the substrate
- -
-
Paragraph 0042
(2017/03/28)
-
- Aryl(triethyl)silanes for Biaryl and Teraryl Synthesis by Copper(II)-Catalyzed Cross-Coupling Reaction
-
Aryl(triethyl)silanes are found to undergo cross-coupling with iodoarenes in the presence of catalytic amounts of CuBr2and Ph-Davephos, as well as cesium fluoride as a stoichiometric base. Because the silicon reagents are readily accessible through catalytic C?H silylation of aromatic substrates, the net transformation allows coupling of aromatic hydrocarbons with iodoarenes via triethylsilylation.
- Komiyama, Takeshi,Minami, Yasunori,Hiyama, Tamejiro
-
supporting information
p. 15787 - 15791
(2016/12/16)
-
- Three-component 2-aryl substituted benzothiophene formation under transition-metal free conditions
-
A base-mediated 2-aryl substituted benzothiophene formation from 2-bromobenzene aldehydes, benzylic esters and elemental sulfur under transition-metal-free conditions is described. Various 2-aryl substituted benzothiophene were efficiently obtained under mild conditions.
- Jiang, Pengcheng,Che, Xingzong,Liao, Yunfeng,Huang, Huawen,Deng, Guo-Jun
-
p. 41751 - 41754
(2016/05/24)
-
- Potassium Hydroxide/Dimethyl Sulfoxide Superbase-Promoted Transition Metal-Free Synthesis of 2-Substituted Benzothiophenes under Visible Light
-
A potassium hydroxide/dimethyl sulfoxide (KOH/DMSO) superbase-promoted method for the synthesis of 2-substituted benzothiophenes has been developed via photoinduced intermolecular annulation of 2-halothioanisoles with terminal alkynes at ambient temperature. The present protocol uses commercially available 2-halothioanisoles as substrates and visible light as energy force, which offers a wide range of benzothiophenes regioselectively in moderate to good yields. Such a facile and effective transformation will provide an environment-friendly approach to the synthesis of benzothiophene derivatives.
- Gao, Li,Chang, Bin,Qiu, Wenzhao,Wang, Lele,Fu, Xianzhi,Yuan, Rusheng
-
p. 1202 - 1207
(2016/04/26)
-
- HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME
-
In the present invention, provided are: a heterocyclic compound which can significantly extend lifespan and improve efficiency, electrochemical stability, and thermal stability of the organic light-emitting device; and an organic light-emitting device containing the heterocyclic compound in an organic compound layer. The heterocyclic compound is represented by chemical formula 1.COPYRIGHT KIPO 2016
- -
-
Paragraph 0168-0171
(2016/10/08)
-
- Bulky α-diimine palladium complexes: Highly efficient for direct C-H bond arylation of heteroarenes under aerobic conditions
-
Through the strategy to enhance the bulkiness on both the backbone and the N-aryl moieties, we designed and synthesized a type of bulky α-diimine palladium complex (i.e., {[Ar-NC(R)-C(R)N-Ar]PdCl2, (Ar = 2-benzhydryl-4,6-dimethylphenyl)}, C1, R = H; C2, R = An; C3, R = Ph). The structures of these palladium complexes were well characterized, while C1 and C3 were further characterized by X-ray diffraction. The catalytic performances of the precatalysts were screened for direct C-H bond arylation of heteroarenes. The bidentate N,N-palladium complex C3 with both a backbone and N-aryl bulkiness was found to be a highly efficient precatalyst under aerobic conditions. With a low palladium loading of 0.5-0.1 mol%, a variety of heteroarenes with challenging bulky steric aryl bromides as well as heteroaryl bromides are all applicable for this cross-coupling reaction.
- Ouyang, Jia-Sheng,Li, Yan-Fang,Shen, Dong-Sheng,Ke, Zhuofeng,Liu, Feng-Shou
-
p. 14919 - 14927
(2016/10/11)
-
- Ligand-Assisted Gold-Catalyzed Cross-Coupling with Aryldiazonium Salts: Redox Gold Catalysis without an External Oxidant
-
Gold-catalyzed C(sp)-C(sp2) and C(sp2)-C(sp2) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With the assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the nitrogen extrusion followed by AuIII reductive elimination as the key step.
- Cai, Rong,Lu, Mei,Aguilera, Ellen Y.,Xi, Yumeng,Akhmedov, Novruz G.,Petersen, Jeffrey L.,Chen, Hao,Shi, Xiaodong
-
supporting information
p. 8772 - 8776
(2015/11/27)
-
- Rh(III)-catalyzed decarboxylative ortho -heteroarylation of aromatic carboxylic acids by using the carboxylic acid as a traceless directing group
-
Highly selective decarboxylative ortho-heteroarylation of aromatic carboxylic acids with various heteroarenes has been developed through Rh(III)-catalyzed two-fold C-H activation, which exhibits a wide substrate scope of both aromatic carboxylic acids and heteroarenes. The use of naturally occurring carboxylic acid as the directing group avoids troublesome extra steps for installation and removal of an external directing group.
- Qin, Xurong,Sun, Denan,You, Qiulin,Cheng, Yangyang,Lan, Jingbo,You, Jingsong
-
supporting information
p. 1762 - 1765
(2015/04/14)
-
- Efficient desulfinative cross-coupling of heteroaromatic sulfinates with aryl triflates in environmentally friendly protic solvents
-
Aryl-substituted heteroaromatics were synthesized via desulfinative cross-coupling reactions using aryl triflate and heteroaromatic sulfinate coupling partners. This method uses synthetically versatile aryl triflates to access aryl-substituted heteroaromatics in good yields employing aqueous and alcoholic media without the use of base, additives or co-catalysts.
- Mangel, Daniel,Buonomano, Cindy,Svigny, Stphane,Di Censo, Gianna,Thevendran, Gowsic,Forgione, Pat
-
p. 1228 - 1239
(2015/03/04)
-
- A family of low molecular-weight, organic catalysts for reductive C-C bond formation
-
Hydrazines form a new family of low molecular-weight reducing agents for diazonium salts. Using only small amounts of hydrazine catalyst, the coupling of diazonium salts to a variety of reactive partners has been achieved, without the requirement for either metal adjuvants or irradiation with visible or ultraviolet light. The generality of the concept proposed herein as well as its advantages in the preparative scale is outlined and discussed.
- Shaaban, Saad,Jolit, Ana?s,Petkova, Desislava,Maulide, Nuno
-
p. 13902 - 13905
(2015/09/15)
-
- Carbocatalysed Oxidative C sp 2 -C sp 2 Homocouplings of Benzo-Fused Heterocycles
-
Appropriate and fine-tuned treatments of amorphous carbon (AC) involving aqua regia or concentrated HNO3 lead to oxidised carbon materials (oAC) which are able to catalyse 2,2′- and 3,3′-homocouplings of various functionalised indoles with outs
- Wirtanen, Tom,M?kel?, Mikko K.,Sarfraz, Jawad,Ihalainen, Petri,Hietala, Sami,Melchionna, Michele,Helaja, Juho
-
supporting information
p. 3718 - 3726
(2016/01/25)
-
- Aerobic and Efficient Direct Arylation of Five-Membered Heteroarenes and Their Benzocondensed Derivatives with Aryl Bromides by Bulky α-Hydroxyimine Palladium Complexes
-
In the present work, a series of α-hydroxyimine palladium complexes with bulky substituents (i.e., {[Ar-N=C(R)-C(R)2-OH]PdCl2} (C1, R = Me, Ar = 2-diphenylmethyl-4,6-dimethylphenyl; C2, R = Me, Ar = 2,6-bis(diphenylmethyl)-4-methylphenyl; C3, R = Me, Ar = 2,6-bis(diphenylmethyl)-4-methyoxylphenyl; C4, R = Me, Ar = 2,6-bis(diphenylmethyl)-4-chlorophenyl; C5, R = Ph, Ar = 2,6-dimethylphenyl; C6, R = Ph, Ar = 2,6-diisopropylphenyl)) were synthesized and characterized. The structures of palladium complexes C1 and C2 were determined by X-ray diffraction. These bidentate N,O-palladium complexes were applied for direct arylation under aerobic conditions. The effects of the reaction conditions and ligand substitution on the catalytic activity were evaluated. Upon a low palladium loading of 0.5 mol %, the bulky palladium complex C6 was successfully used to catalyze the cross-coupling of a variety of five-membered heteroarenes and their benzo-condensed derivatives with (hetero)aryl bromides. The mechanistic investigation on the direct arylation supported the involvement of a Pd(0)/Pd(II) CMD process.
- Luo, Bao-Tian,Liu, Huan,Lin, Zhi-Jie,Jiang, Jingxing,Shen, Dong-Sheng,Liu, Rui-Zhi,Ke, Zhuofeng,Liu, Feng-Shou
-
p. 4881 - 4894
(2015/11/09)
-
- Synthesis, characterization and X-ray structures of N-heterocyclic carbene palladium complexes based on calix[4]arenes: Highly efficient catalysts towards Suzuki-Miyaura cross-coupling reactions
-
A new series of calix[4]arene supported N-heterocyclic carbene palladium complexes were developed and fully characterized. A mono-substituted calix[4]arene was prepared through conventional procedures, following with the attachment of imidazolyl derivative groups to compose the precursors of novel NHCs ligands. Undergoing the alkylation with n-butylbromide and corresponding metallation with palladium and pyridine, original complexes were obtained. After a full characterization in solution and solid state, the evaluation of catalytic activity was taken out in Suzuki-Miyaura cross-coupling reactions, which revealed good performances.
- Ren, Hui,Xu, Yong,Jeanneau, Erwann,Bonnamour, Isabelle,Tu, Tao,Darbost, Ulrich
-
p. 2829 - 2837
(2014/04/17)
-
- Discovery of synthetic leishmania inhibitors by screening of a 2-arylbenzothiophene library
-
Tamoxifen has been shown to be active in vitro against Leishmania and effective in the treatment for leishmaniasis in murine models. Through the screening of a compound library of estrogen receptor modulator analogs, we identified the major characteristic
- Bonano, Vivian I.,Yokoyama-Yasunaka, Jenicer K.U.,Miguel, Danilo C.,Jones, Scott A.,Dodge, Jeffrey A.,Uliana, Silvia R.B.
-
p. 289 - 296
(2014/03/21)
-
- Direct arylation of benzo[b]furan and other benzo-fused heterocycles
-
The direct arylation of benzo[b]furan, benzo[b]thiophene, and indole has been studied by using aromatic bromides as the aryl source. The protocol employing common reagents and a Pd catalyst has led to the regioselective arylation of these heterocycles at the 2-position. A range of functional groups were tolerated, providing quick access to a variety of arylated benzo-fused heterocycles that would be accessible more elaborately using classical synthetic strategies. This is the first systematic study of the direct arylation of benzo[b]-furan.
- Dao-Huy, Toan,Haider, Maximilian,Glatz, Fabian,Schnürch, Michael,Mihovilovic, Marko D.
-
supporting information
p. 8119 - 8125
(2015/01/09)
-
- A simple catalytic system based on PdCl2(CH3CN) 2 in water for cross-coupling reactions using diazonium salts
-
Aryl-heteroaryl and heteroaryl-heteroaryl compounds are obtained through the Suzuki-Miyaura cross-coupling reactions between diazonium salts and potassium trifluoroborates using PdCl2(CH3CN)2 as the catalyst in water and in the absence of any additive, ligand or base. In addition, the same mild catalytic system is effective for the Matsuda-Heck reaction between several monoolefins with aryldiazonium salts.
- El Bakouri, Ouissam,Fernández, Martí,Brun, Sandra,Pla-Quintana, Anna,Roglans, Anna
-
p. 9761 - 9765
(2013/10/22)
-
- Copper-catalyzed synthesis of benzo[ b ]thiophenes and benzothiazoles using thiocarboxylic acids as a coupling partner
-
An efficient copper-catalyzed approach to benzo[b]thiophene and benzothiazole derivatives using thiocarboxylic acids as a sulfur source has been developed. In the presence of CuI and 1,10-phen, and n-Pr3N as the base, (2-iodobenzyl)triphenylphosphonium bromide and (2-iodophenylimino) triphenylphosphorane reacted smoothly with thiocarboxylic acids to give benzo[b]thiophene and benzothiazole derivatives in good yields via sequential Ullmann-type C-S bond coupling and Wittig condensation.
- Yu, Hui,Zhang, Meishu,Li, Yuzhe
-
p. 8898 - 8903
(2013/09/24)
-
- Transition-metal-free method for the synthesis of benzo[b]thiophenes from o -halovinylbenzenes and K2S via direct SNAr-type reaction, cyclization, and dehydrogenation process
-
A new, highly efficient procedure for the synthesis of benzothiophenes from easily available o-halovinylbenzenes and potassium sulfide has been developed. The reaction tolerated a wide range of functionalities, and various 2-substituted benzo[b]thiophenes
- Zhang, Xiaoyun,Zeng, Weilan,Yang, Yuan,Huang, Hui,Liang, Yun
-
p. 1687 - 1692
(2013/09/02)
-
- Pd-catalyzed β-selective direct C-H bond arylation of thiophenes with aryltrimethylsilanes
-
Direct arylation of thiophenes and benzothiophenes with aryltrimethylsilanes was effectively catalyzed by PdCl2(MeCN) 2 in the presence of CuCl2 as an oxidant. The reaction preferentially occurred at the β-position of both
- Funaki, Kenji,Sato, Tetsuo,Oi, Shuichi
-
supporting information
p. 6186 - 6189
(2013/02/23)
-
- Visible light photocatalytic synthesis of benzothiophenes
-
The photocatalytic reaction of o-methylthio-arenediazonium salts with alkynes yields substituted benzothiophenes regioselectively through a radical annulation process. Green light irradiation of eosin Y initiates the photoredox catalysis. The scope of the reaction was investigated by using various substituted diazonium salts and different alkynes.
- Hari, Durga Prasad,Hering, Thea,Koenig, Burkhard
-
p. 5334 - 5337,4
(2012/12/12)
-
- Generation of metalated thiophenes with Grignard reagent and catalytic secondary amine for the cross coupling reaction with aryl halides
-
The reaction of thiophene derivatives with Grignard reagent (EtMgCl) and a catalytic amount of amine (Cy2NH) induced the metalation at the α-position. Following addition of several aryl halides in the presence of a nickel or palladium catalyst afforded C-H arylated products in good to excellent yields. The method was successfully applied to facile synthesis of differently-substituted 2,5-diarylthiophenes.
- Tanaka, Shota,Tanaka, Daiki,Sugie, Atsushi,Mori, Atsunori
-
experimental part
p. 1173 - 1176
(2012/03/26)
-
- Flash generation of a highly reactive Pd catalyst for suzuki-miyaura coupling by using a flow microreactor
-
Superflash! Flash chemistry enables the use of highly reactive unstable species as catalysts for chemical synthesis. Fast micromixing of a solution of [Pd(OAc)2] and that of tBu3P in 1:1 mole ratio gave a solution of a highly reactive unstable species, which was immediately transferred to a vessel by using a flow microreactor, in which Suzuki-Miyaura coupling was conducted (see scheme). Copyright
- Nagaki, Aiichiro,Takabayashi, Naofumi,Moriwaki, Yuya,Yoshida, Jun-Ichi
-
supporting information
p. 11871 - 11875
(2012/10/29)
-
- Extending the utility of [Pd(NHC)(cinnamyl)Cl] precatalysts: Direct arylation of heterocycles
-
The use of [Pd(NHC)(cinnamyl)Cl] precatalysts in the direct arylation of heterocycles has been investigated. Among four different precatalysts, [Pd(SIPr)(cinnamyl)Cl] proved to be the most efficient promoter of the reaction. The C-H functionalization of sulfuror nitrogen-containing heterocycles has been achieved at low catalyst loadings. These catalyst charges range from 0.1 to 0.01 mol % palladium.
- Martin, Anthony R.,Chartoire, Anthony,Slawin, Alexandra M.Z.,Nolan, Steven P.
-
supporting information
p. 1637 - 1643
(2012/11/07)
-
- A practical, one-pot synthesis of highly substituted thiophenes and benzo[b]thiophenes from bromoenynes and o-alkynylbromobenzenes
-
An efficient synthesis of thiophenes and benzo[b]thiophenes has been developed from easily available bromoenynes and o-alkynylbromobenzene derivatives. This novel one-pot procedure involves a Pd-catalyzed C-S bond formation using a hydrogen sulfide surrogate followed by a heterocyclization reaction. Moreover, in situ functionalization with selected electrophiles further expands the potential of this methodology to the preparation of the corresponding highly substituted sulfur heterocycles.
- Guilarte, Veronica,Fernandez-Rodriguez, Manuel A.,Garcia-Garcia, Patricia,Hernando, Elsa,Sanz, Roberto
-
p. 5100 - 5103
(2011/11/29)
-
- Palladium-catalyzed C-S coupling: Access to thioethers, benzo[b]thiophenes, and thieno[3,2-b]thiophenes
-
The first C-S bond formation/cross-coupling/cyclization domino reaction using thiourea as a cheap and easy to handle dihydrosulfide surrogate has been developed. Structurally important biarylthioether, benzo[b]thiophenes, and thieno[3,2-b]thiophene scaffolds are provided in high yield.
- Kuhn, Marius,Falk, Florian C.,Paradies, Jan
-
supporting information; experimental part
p. 4100 - 4103
(2011/10/08)
-
- CuI/TMEDA-catalyzed annulation of 2-bromo alkynylbenzenes with Na 2S: Synthesis of benzo[b]thiophenes
-
A copper-catalyzed thiolation annulation reaction of 2-bromo alkynylbenzenes with sodium sulfide has been developed. In the presence of CuI and TMEDA, a variety of 2-substituted benzo[b]thiophenes were readily prepared in moderate to good yields by the reaction of 2-bromo alkynylbenzenes and Na2S?9H2O.
- Sun, Lei-Lei,Deng, Chen-Liang,Tang, Ri-Yuan,Zhang, Xing-Guo
-
experimental part
p. 7546 - 7550
(2011/11/29)
-
- Palladium-catalyzed direct arylation of heteroaromatic compounds: Improved conditions utilizing controlled microwave heating
-
A versatile and rapid microwave-assisted procedure for the palladium-catalyzed direct arylation of heterocycles by aryl bromides and heteroaryl bromides is described. This novel protocol features short coupling times (10-60 min) and low catalyst loadings
- Baghbanzadeh, Mostafa,Pilger, Christian,Oliver Kappe
-
experimental part
p. 8138 - 8142
(2011/11/07)
-
- One-pot synthesis of amine-substituted aryl sulfides and benzo[ b ]thiophene derivatives
-
A series of amine-substituted aryl sulfides have been synthesized from nitroaryl halides via a simple one-pot procedure involving metal-free C-S cross-coupling and in situ nitro group reduction. Various nitroaryl halides were reacted with thiols in recyclable poly(ethylene glycol) to afford the amine-substituted aryl sulfides in high yield. Additionally, the cross-coupling reactions of nitro- and aldehyde-substituted aryl halides with benzyl thiols under the same reaction conditions were demonstrated to afford benzothiazole and phenylbenzo[b]thiophene derivatives.
- Duan, Zhongyu,Ranjit, Sadananda,Liu, Xiaogang
-
supporting information; experimental part
p. 2430 - 2433
(2010/07/10)
-
