- 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
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p. 653 - 656
(2020/12/23)
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- 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
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p. 2469 - 2474
(2021/08/06)
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- Infrared Irradiation-Assisted Solvent-Free Pd-Catalyzed (Hetero)aryl-aryl Coupling via C?H Bond Activation
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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.
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p. 3391 - 3401
(2021/07/28)
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- Trithiocarbonate Anion as a Sulfur Source for the Synthesis of 2,5-Disubstituted Thiophenes and 2-Substituted Benzo[ b]thiophenes
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The trithiocarbonate anion (CS32-) was generated in situ from CS2 and KOH in dimethyl sulfoxide by a simple method and used as a novel synthetic equivalent of the S2- synthon for the synthesis of 2,5-disubstituted thiophenes from 1,3-butadiynes. Additionally, this system was employed for the metal-free synthesis of 2-substituted benzo[b]thiophenes from 2-haloalkynyl (hetero)arenes. These compounds were obtained from a cheap and readily available sulfur source in moderate to good yields, with good functional group tolerance.
- Paix?o, Douglas B.,Rampon, Daniel S.,Salles, Helena D.,Soares, Eduardo G. O.,Bilheri, Filipe N.,Schneider, Paulo H.
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p. 12922 - 12934
(2020/11/26)
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- Synthesis of Enaminone-Pd(II) Complexes and Their Application in Catalysing Aqueous Suzuki-Miyaura Cross Coupling Reaction
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A series of Pd(II)-enaminone complexes, termed Pd(eao)2, have been synthesized and characterized. The investigation on the catalytic activities of these new Pd(II)-reagents has proved that the Pd(eao)2-1 possesses excellent catalytic activity for the Suzuki- Miyaura cross coupling reactions of aryl bromides/chlorides with aryl/vinyl boronic acids in the environmentally benign media of aqueous PEG400 at low loading (5 mol‰). The superiority of this Pd(II)-reagent to those commercial Pd(II) and Pd(0) catalysts in catalyzing the reactions has been confirmed by parallel experiments. What's more, Pd(eao)2-2 has been found as a practical catalyst for the homo-coupling reactions of aryl boronic acids.
- Fu, Leiqing,Cao, Xiaoji,Wan, Jie-Ping,Liu, Yunyun
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p. 254 - 258
(2020/01/25)
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- Nickel-catalyzed and Li-mediated regiospecific C-H arylation of benzothiophenes
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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.
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p. 3155 - 3161
(2020/06/19)
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- 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)
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- Method for preparing benzothiophene compounds by silver oxide catalysis method
-
The invention provides a method for preparing benzothiophene compounds through a silver oxide catalysis method, and belongs to the technical field of heterocyclic compound preparation. In the presenceof an acidic solvent, the 2-acetenyl diphenyl sulfide a
- -
-
Paragraph 0072-0077
(2019/12/02)
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- 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
-
supporting information
p. 9279 - 9284
(2019/01/03)
-
- 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)
-
- 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)
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- 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; 0049
(2018/08/28)
-
- Method for synthesizing benzothiophene derivatives from dihaloarene under microwave irradiation under catalysis of copper
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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; 0053
(2018/09/08)
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- 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)
-
- 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)
-
- Synthesis of 3-Substituted 2-Arylpyridines via Cu/Pd-Catalyzed Decarboxylative Cross-Coupling of Picolinic Acids with (Hetero)Aryl Halides
-
A decarboxylative cross-coupling of 3-substituted picolinic acids with (hetero)aryl halides is presented. In the presence of catalytic Cu2O and Pd(1,5-cyclooctadiene)Cl2 with 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl as the ligand, both electron-rich and electron-deficient aryl bromides and chlorides as well as heteroaryl bromides were successfully coupled with various picolinate salts under mild conditions in yields up to 96%. This protocol provides an efficient entry to 2-(hetero)arylpyridines, an attractive substance class in drug discovery.
- Hackenberger, Dagmar,Weber, Philip,Blakemore, David C.,Goossen, Lukas J.
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p. 3917 - 3925
(2017/04/11)
-
- 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)
-
- 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 0044
(2017/03/28)
-
- 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)
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- 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
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p. 1202 - 1207
(2016/04/26)
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- A robust and efficient catalyst possessing an electron-deficient ligand for the palladium-catalyzed direct arylation of heteroarenes
-
The exploration of the direct arylation capacity of a unique, thermally stable, and air-stable Pd0-phosphine catalyst is reported. Besides decisively contributing to catalyst robustness, the electron-deficient trifluoromethyl-substituted triphenylphosphine ligands make the palladium center more electron-deficient and accelerate the direct arylation step. The combination of only 0.5-2 mol-% of the catalyst and a substoichiometric quantity of pivalic acid generates an efficient system to promote biaryl-forming reactions of a broad range of electronically varied hetarenes and aryl bromides. The observed regioselective arylations suggest that a concerted metalation-deprotonation pathway is involved in the C-H activation step.
- Jakab, Alexandra,Dalicsek, Zoltn,Sos, Tibor
-
supporting information
p. 56 - 59
(2015/02/19)
-
- 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)
-
- Cu-catalyzed in situ generation of thiol using xanthate as a thiol surrogate for the one-pot synthesis of benzothiazoles and benzothiophenes
-
A new copper-catalyzed in situ generation of aryl thiolates strategy was successfully developed for the one-pot synthesis of substituted benzothiazoles from 2-iodoanilides using xanthate as a thiol precursor. A wide range of 2-iodoanilides with both electron-releasing and electron-withdrawing groups produced the corresponding benzothiazoles in good yields. Further, this one-pot protocol was successfully utilized for the synthesis of a potent antitumor agent 2-(3,4-dimethoxyphenyl)-5-fluorobenzo[d]thiazole (PMX 610). Finally, the copper-catalyzed in situ generation of aryl thiolates strategy was successfully applied for the domino synthesis of substituted benzothiophenes from o-haloalkynyl benzenes using xanthate as a thiol precursor.
- Prasad,Sekar
-
p. 1659 - 1665
(2013/03/28)
-
- Phosphine-free palladium-catalysed direct C2-arylation of benzothiophenes with aryl bromides
-
Ligand-free Pd(OAc)2 was found to catalyse very efficiently the direct C2-arylation of benzothiophene derivatives under low catalyst concentration. The reaction can be performed employing as little as 0.5-0.1 mol % catalyst with electron-deficient and some electron-rich aryl bromides. The presence of a methyl or a formyl substituent at C3 of benzothiophene has a minor influence on the reactivity, and even a bromo substituents at C3 is tolerated. A wide variety of functional groups on the aryl bromide, such as nitrile, nitro, acetyl, formyl, ester, chloro, fluoro or trifluoromethyl has been employed.
- Zhao, Liqin,Bruneau, Christian,Doucet, Henri
-
p. 7082 - 7089
(2013/07/26)
-
- 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)
-
- 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)
-
- 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)
-
- 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
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p. 5334 - 5337,4
(2012/12/12)
-
- 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
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supporting information; experimental part
p. 2430 - 2433
(2010/07/10)
-
- Palladium-catalyzed C-H functionalization of heteroarenes with aryl bromides and chlorides
-
Palladium-catalyzed C-H arylation of electron-enriched heteroarenes with aryl bromides and aryl chlorides proceeds in the presence of LiO-t-Bu as a base. The reaction allows one-pot synthesis of differently substituted 2,5-diarylthiazole with the same catalyst system by switching the solvent and the amount of base.
- Tamba, Shunsuke,Okubo, Youhei,Tanaka, Shota,Monguchi, Daiki,Mori, Atsunori
-
supporting information; experimental part
p. 6998 - 7001
(2010/11/24)
-
- Establishment of broadly applicable reaction conditions for the palladium-catalyzed direct arylation of heteroatom-containing aromatic compounds
-
Conditions for the palladium-catalyzed direct arylation of a wide range of heterocycles with aryl bromides are reported. Those conditions employ a stoichiometric ratio of both coupling partners, as well as a substoiehiometric quantity of pivalic acid, which results in significantly faster reactions. An evaluation of the influence of the nature of the aryl halide has also been carried out.
- Liegault, Benoit,Lapointe, David,Caron, Laurence,Vlassova, Anna,Fagnou, Keith
-
scheme or table
p. 1826 - 1834
(2009/07/01)
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- Selective palladium-catalysed ipso arylation of α,α- disubstituted benzo[b]thien-2-ylmethanols with aryl bromides using PCy 3 as ligand
-
α,α-Diphenylbenzo[b]thien-2-ylmethanol was treated with a series of aryl bromides in the presence of palladium(II) acetate and tricyclohexylphosphane to give the appropriate 2-aryl-benzo[b]thiophenes in good to excellent yield with concomitant formation o
- Biro, A. Beatrix,Kotschy, Andras
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p. 1364 - 1368
(2008/09/18)
-