- Polyaniline-Induced Arylation with Arenediazonium Salts Derived from Anilines
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A catalytic amount of a reduced form of polyaniline (a redox-active π-conjugated polymer) was found to induce C?H direct arylation of (hetero)arenes with arenediazonium salts prepared from anilines with methanesulfonic acid (MeSO3H) and tert-butyl nitrite (tBuONO). The difficult part of this method is the coexistence of an oxidant and a reductant in this sequential diazotization and arylation system; diazotization requires weak oxidants such as alkyl nitrites, whereas the arylation is induced by a reductant. This was achieved by the careful control of the amount of tBuONO (1.0 equivalent) for the diazotization step, and sequential arylation using 5 mol % of the polyaniline. The reaction took place under mild conditions without any metals or strong bases at room temperature, and the amino group is a formal leaving group. The scope of the substrates demonstrates the versatility in the combination of anilines with a variety of functional groups and several (hetero)arenes. Two-directional arylation for the synthesis of an unsymmetrical 1,4-diarylated (furyl and pyrrolyl groups) benzene was achieved, using mono-Boc-protected 1,4-phenylenediamine as a substrate. This shows potential for the synthesis of more complicated oligoarene compounds.
- Hata, Dai,Moriuchi, Toshiyuki,Hirao, Toshikazu,Amaya, Toru
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- Designing a heterogeneous Pd(ii)-NHC-based C-H activation catalyst on a self-supported coordination polymer platform
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In this work, we report a single-site, heterogeneous Pd(ii)-NHC-based oxidative C-H activation catalyst, designed on a self-supported coordination polymer platform. The system has been applied successfully for selective arene C-H monohalogenation reactions affording a good degree of efficiency and reusability. Control experiments suggested that the Ru(ii)-terpyridine-based coordination network scaffolding the covalently attached Pd(ii)-NHC catalytic centres was highly robust under oxidizing conditions and rendered superior activity than the homogeneous counterpart.
- Mondal, Moumita,Joji, Jinu,Choudhury, Joyanta
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- Black phosphorus as a metal-free, visible-light-active heterogeneous photoredox catalyst for the direct C-H arylation of heteroarenes
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Black phosphorus (BP) is for the first time employed as a metal-free, heterogeneous photoredox catalyst for the direct C-H arylation of heteroarenes with aryl diazonium salts. The arylated heteroarenes are obtained in moderate to good yields under visible-light illumination, and the protocol is shown to be applicable for the scale-up synthesis.
- Kalay, Erbay,Kü?ükke?eci, Hüseyin,Kilic, Haydar,Metin, ?nder
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- Visible-Light-Promoted Arylation Reactions Photocatalyzed by Bismuth(III) Oxide
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Bismuth(III) oxide has been successfully applied as a photocatalyst in the arylation of heteroarenes with diazonium salts. With a low catalyst loading (1 to 5 mol-%), this cheap and nontoxic semiconductor could efficiently promote the formation of the aryl radical under visible light irradiation. The arylated products are obtained in moderate to good yields, and the process admits straightforward scale-up (10 mmol; 1 mol-% Bi2O3). In two cases, the diazonium salt was generated in situ and used in the photocatalytic arylation in a tandem manner. Besides heteroarenes, Bi2O3 also catalyzed the arylation of differently substituted alkenes and alkynes, thus representing a viable and practical alternative to the more commonly used ruthenium complexes and organic dyes.
- Buglioni, Laura,Riente, Paola,Palomares, Emilio,Pericàs, Miquel A.
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- Analysis of the Carbon and Proton NMR Spectra of 2-Arylthiophenes and Related Heterocycles
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Complete proton and carbon NMR assignments were made for five 2-(2-X-phenyl)thiophenes (X = NH2, NO2, COOH, Br), four 2,5-diphenylheterocycles (thiophene, furan and N-methyl- and N-phenylpyrrole) and N-phenylpyrrole using HETCOR, COSY, XCORFE and, in one
- Mazza, Dario Del,Reinecke, Manfred G.,Smith, William B.
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- Tris-NHC-propagated self-supported polymer-based Pd catalysts for heterogeneous C-H functionalization
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Three-dimensionally propagated imidazolium-containing mesoporous coordination polymer and organic polymer-based platforms were successfully exploited to develop single-site heterogenized Pd-NHC catalysts for oxidative arene/heteroarene C-H functionalization reactions. The catalysts were efficient in directed arene halogenation, and nondirected arene and heteroarene arylation reactions. High catalytic activity, excellent heterogeneity and recyclability were offered by these systems making them promising candidates in the area of heterogeneous C-H functionalization, where efficient catalysts are still scarce.
- Choudhury, Joyanta,Dutta, Tapas Kumar,Mandal, Tanmoy,Mohanty, Sunit
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supporting information
p. 10182 - 10185
(2021/10/12)
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- Further lead optimization on Bax activators: Design, synthesis and pharmacological evaluation of 2-fluoro-fluorene derivatives for the treatment of breast cancer
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To further pursue potent Bax activators with better safety profiles for the treatment of breast cancer, structural optimization was conducted based on lead compound CYD-4-61 through several strategies, including scaffold hopping on the 2-nitro-fluorene ring, replacement of the nitro group with bioisosteres to avoid potential toxicity, and further optimization on the upper pyridine by exploring diverse alkylamine linkers as a tail or replacing the pyridine with bioisosteric heterocycles. F-containing compound 22d (GL0388) exhibited a good balance between the activity and toxicity, displaying submicromolar activities against a variety of cancer cell lines with 5.8–10.7-fold selectivity of decreased activity to MCF-10A human mammary epithelial cell line. Compound 22d dose-dependently blocked colony formation of breast cancer cells and prevented the migration and invasion of MDA-MB-231 cells. Mechanism of action studies indicate that 22d activated Bax, rendering its insertion into mitochondrial membrane, thereby leading to cytochrome c release from the mitochondria into the cytoplasm, subsequently inducing release of apoptotic biomarkers. Further in vivo efficacy studies of 22d in human breast cancer xenografts arisen from MDA-MB-231 cells demonstrated that this drug candidate significantly suppressed tumor growth, indicating the therapeutic promise of this class of compounds for the treatment of breast cancer as well as the potential for developing F-radiolabeled imaging ligands as anticancer chemical probes.
- Liu, Gang,Kim, Hyejin,Wang, Pingyuan,Fricke, Doerte R.,Chen, Haiying,Wang, Tianzhi,Shen, Qiang,Zhou, Jia
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- Hypercrosslinked Polymer Platform-Anchored Single-Site Heterogeneous Pd-NHC Catalysts for Diverse C-H Functionalization
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We demonstrate a new class of hypercrosslinked polymer (HCP) platform-Anchored single-site heterogenized Pd-NHC catalysts for multipurpose C-H functionalization reactions. This new class is represented by a set of three catalysts, viz., HCP-B-MeNHC-Pd, HCP-B-BnNHC-Pd, and HCP-TPM-MeNHC-Pd, having a variation on the structural feature of the anchoring polymeric platform. All three catalysts were fully characterized via diverse solid-state characterization and analytical techniques such as X-ray photoelectron spectroscopy, 13C cross-polarization magic-Angle-spinning nuclear magnetic resonance, field-emission scanning electron microscopy, energy-dispersive X-ray analysis, thermogravimetric analysis, and inductively coupled plasma-optical emission spectrometry. Three types of regularly practiced and very useful C-H functionalization reactions, viz., C-H halogenation, acetoxylation, and arylation, are tested with the new catalysts and found to be highly compatible and successful. With the HCP-TPM-MeNHC-Pd catalyst, up to 85, 75, and 70% yields of the functionalized products were achieved for the halogenation, acetoxylation, and arylation reactions, respectively. Demanding attributes such as enhanced activity, heterogeneity, and recyclability are offered by this new system, making it a promising candidate in the field of heterogeneous C-H functionalization, where only a few efficient catalysts are available.
- Mandal, Tanmoy,Mondal, Moumita,Choudhury, Joyanta
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supporting information
p. 2443 - 2449
(2021/08/03)
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- Bis-tri-aromatic amine compound containing spiral structure, application and light emitting diode
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The invention provides a bis-tri-aromatic amine compound containing a spiral structure. The compound has the structural formula as shown in the figure I in the specification. The compound has relatively good heat stability, high light-emitting efficiency
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Paragraph 0049; 0050; 0051; 0052; 0053
(2019/02/25)
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- Ditriaromatic amine compound containing five-membered ring spiral structure, application thereof and light-emitting device
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The invention provides a ditriaromatic amine compound containing a five-membered ring spiral structure, which has a following structural formula shown as the specification. The compound has good thermal stability, high luminous efficiency and high lumines
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Paragraph 0050; 0052; 0053; 0054
(2019/04/10)
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- Compound containing pentacyclic ring screw structure and organic electroluminescence device
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The invention provides an organic electroluminescence compound containing a pentacyclic ring screw structure. The compound has good heat stability, high luminous efficiency, high luminous purity and low driving voltage, can be used for manufacturing an organic electroluminescence device and is applied to the fields of organic solar cells or perovskite batteries or organic thin-film transistors or organic photoreceptors. The invention further provides the organic electroluminescence device. The organic electroluminescence device comprises an anode, a cathode and an organic layer, the organic layer comprises at least one layer of a light-emitting layer, a hole injection layer, a hole transmission layer, a laser barrier layer and an electronic transmission layer, and at least one layer in the organic layer contains the compound shown in the structural formula I. The structural formula I is shown in the specification.
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Paragraph 0049; 0050; 0051
(2017/08/28)
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- Rh-Catalyzed Dehydrogenative Cyclization Leading to Benzosilolothiophene Derivatives via Si-H/C-H Bond Cleavage
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Straightforward syntheses leading to π-extended benzosilolothiophene (BST) derivatives by Rh-catalyzed dehydrogenative cyclization reactions have been developed. Electron-deficient ligands were effective for the reactions, and dppe-F20 gave the
- Mitsudo, Koichi,Tanaka, Seiichi,Isobuchi, Ryota,Inada, Tomohiro,Mandai, Hiroki,Korenaga, Toshinobu,Wakamiya, Atsushi,Murata, Yasujiro,Suga, Seiji
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supporting information
p. 2564 - 2567
(2017/05/24)
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- Modular Construction of Fluoroarenes from a New Difluorinated Building Block by Cross-Coupling/Electrocyclisation/Dehydrofluorination Reactions
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Palladium-catalysed coupling reactions based on a novel and easy-to-synthesise difluorinated organotrifluoroborate were used to assemble precursors to 6π-electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 °C, depending on the central component of the π-system; nonaromatic trienes were most reactive, but even systems that required the temporary dearomatisation of two arenyl subunits underwent electrocyclisation, albeit at elevated temperatures. Photochemical conditions were effective for these more demanding reactions. The package of methods delivered a structurally diverse set of fluorinated arenes, spanning a 20 kcal mol?1range of reactivity, by a flexible route.
- Percy, Jonathan M.,Emerson, Helena,Fyfe, James W. B.,Kennedy, Alan R.,Maciuk, Sergej,Orr, David,Rathouská, Lucie,Redmond, Joanna M.,Wilson, Peter G.
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supporting information
p. 12166 - 12175
(2016/08/16)
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- Catalytic chemical amide synthesis at room temperature: One more step toward peptide synthesis
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An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.
- Mohy El Dine, Tharwat,Erb, William,Berhault, Yohann,Rouden, Jacques,Blanchet, Jér?me
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p. 4532 - 4544
(2015/05/13)
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- AgONO-Assisted Direct C-H Arylation of Heteroarenes with Anilines
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A novel copper-catalyzed C-H arylation of heteroarenes with anilines by an in situ diazonium reaction is established by using silver nitrite (AgONO) as an unconventional nitrosating reagent under acid-free conditions. It provides a complementary approach for the C-H arylation of electron-rich heteroarenes with aromatic amines affording a variety of heterobiaryls in moderate to good yields.
- Gowrisankar, Saravanan,Seayad, Jayasree
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supporting information
p. 12754 - 12758
(2015/03/30)
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- Copper-catalyzed cross-coupling of aryl- and heteroaryltriethoxysilanes with aryl and heteroaryl iodides and bromides
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Copper(I)-catalyzed coupling of aryl- and heteroaryltriethoxysilanes with aryl and heteroaryl iodides is described. The transformation also proceeds with activated aryl bromides, but in this case it requires a stoichiometric amount of the catalyst for best product yields. The current reaction requires a P,N-based bidentate ligand for aryl-aryl coupling while it proceeds without external ligands for aryl-heteroaryl coupling to afford good product yields. The reaction protocol can also be applied to achieve biarylation of diiodoarenes in reasonable yields. Georg Thieme Verlag Stuttgart New York.
- Gurung, Santosh K.,Thapa, Surendra,Shrestha, Bijay,Giri, Ramesh
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p. 1933 - 1937
(2014/07/22)
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- Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2)-H activation/C-O formation
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We report an efficient Pd-catalyzed C(sp2)-H activation/C-O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(aryl)arylphosphonic acid monoethyl esters under aerobic conditions.
- Shin, Seohyun,Kang, Dongjin,Jeon, Woo Hyung,Lee, Phil Ho
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supporting information
p. 1220 - 1227
(2014/06/10)
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- A straightforward anionic coupling for the synthesis of ortho-bromobiaryls
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Non-catalyzed anionic coupling of aryllithiums with 1,2-dibromobenzene gives straightforward access to valuable ortho-bromobiaryls.
- Becht, Jean-Michel,Ngouela, Silvère,Wagner, Alain,Mioskowski, Charles
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p. 6853 - 6857
(2007/10/03)
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- Generation of aryl radicals from arylboronic acids by manganese(III) acetate: Synthesis of biaryls and heterobiaryls
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The efficient generation of aryl radicals from arylboronic acids by manganese(III) acetate is described. In aromatic solvents, in situ generated aryl radicals afford the corresponding biaryls in very good yields. This method works selectively, and yields
- Demir, Ayhan S.,Reis, Oemer,Emrullahoglu, Mustafa
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p. 578 - 580
(2007/10/03)
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- Manganese(III) acetate-mediated oxidative coupling of phenylhydrazines with furan and thiophene: A novel method for hetero biaryl coupling
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A convenient new method for the arylation of furan and thiophene with arylhydrazine and manganese(III) acetate is described. Oxidation of arylhydrazines with Mn(III) acetate in furan or thiophene affords the corresponding 2-aryl-substituted furans and thiophenes in good yield using commercially available materials; access to 2-substituted heterobiaryls works selectively, and coupling occurs with loss of the hydrazine moiety.
- Demir, Ayhan S.,Reis, ?mer,Emrullaho?lu, Mustafa
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p. 8055 - 8058
(2007/10/03)
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- Benzo-fused lactams promote release of growth hormone
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There are disclosed certain novel compounds identified as benzo-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible meat products more efficient, and in humans, to increase the stature of those afflicted with a lack of a normal secretion of natural growth hormone. The compounds are prepared by substitution of an amino-lactam with a substituted amide function. Growth promoting compositions containing such bezno-fused lactams as the active ingredient thereof are also disclosed. STR1 where L is STR2
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- Potentially Aromatic Thiophenium Ylides. V. Reactions of Ethoxycarbonyl- (and Methoxycarbonyl)-2-(2-thienyl)phenylcarbene
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In an attempt to make thiophenium ylides in which the ylide bond is part of a five-membered ring annulated to the α-side of the thiophene moiety, two alkoxycarbonyl substituted 2-(2-thienyl)phenylcarbenes have been made, with and without chlorine substituents in the remaining thiophene positions.With rhodium acetate as a catalyst the carbene without chlorines cyclized to the 3-position of the thiophene to give a fluorene analogue, whereas no cyclization was detected when the 3-position was blocked.
- Solbakken, Magne,Skramstad, Jan
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p. 1214 - 1220
(2007/10/02)
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- Potentially Aromatic Thiophenium Ylides 3. Cyclization of 2-(2'-Thienyl)benzoylcarbene
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Catalytic decomposition of 2(2'-diazoacetylphenyl)thiophene gives the 4,10b-dihydro-indacyclopropathiophen-6-one (5) and the naphthothiophen-5-ol (6).It is shown that 5 rearranges to 6 under acid catalysis.The mechanisms for the r
- Storflor, Harry,Skramstad, Jan
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p. 178 - 183
(2007/10/02)
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- Potentyally Aromatic Thiophenium Ylides 4. Formation and Cyclization of Methyl and Methoxycarbonyl Substituted 2-(2'-Thienyl)benzoylcarbenes
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The catalytic decomposition of methyl- and methoxycarbonyl substituted 2-(2'-diazoacetylphenyl)thiophenes has been studied.The products are accounted for by assuming a primary formation of bicyclic thiophenium ylides.The ylides rearrange to thiopyrans, sp
- Storflor, Harry,Skramstad, Jan
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p. 303 - 309
(2007/10/02)
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