- Synthesis of para-substituted 3-formyl arylboronic esters
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The synthesis of novel para-substituted amino- and phenoxy-3-formylarylboronic acids is described. These compounds are formed by the hitherto unreported nucleophilic aromatic substitution of fluorine with a range of phenols and amines in the presence of a boronic acid moiety. These reactions proceed in moderate to good yields (37-92%) and provide a useful regioselective synthetic route to trisubstituted arylboronates. These compounds are important both as intermediates in organic synthesis and as end products in their own right.
- Holland, Richard,Spencer, John,Deadman, John J.
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- Novel β?hydroxy ketones: Synthesis, spectroscopic characterization, molecular docking, and anticancer activity studies
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In this study, a series of novel β?hydroxy ketone derivatives 3a-o were designed, synthesized, and evaluated for their anticancer activity. The structure of these compounds were characterized by IR, 1H and 13C NMR, mass spectrometry and elemental analysis methods. All the synthesized compounds were screened for anticancer activity against MCF-7 and U87 cells. Among them, compound 3l was appeared to be the most potent compound on both cancer cells; and IC50 dose was determined as 145 μM for MCF-7 cells and 6,6 μM for U87 cells. DNA ladder and Annexin V apoptotic marker tests were used and as a result, 3l caused the initiation of apoptosis on U87 cells. VDAC protein expression increased dramatically after U87 glioblastoma brain cancer cells were treated with compound 3l Additionally, the molecular modeling of these compounds was studied in FLT3 receptor, Estrogen receptor, and PARP2 receptor for the treatment of Acute Myeloid Leukemia (AML), breast cancer, and Glioblastoma (GBM) respectively. Their binding motifs and drug-like properties were investigated, and the results are highlighted in the discussion. Based on the results, compound 3l may have a potential drug candidate profile that can reverse the drug resistance profile.
- Guzel, Mustafa,Kanturk, Gokhan,Kucuk, Hatice Baspinar,Senturk, Ahmet Mesut,Yerlikaya, Serife,Yildiz, Tulay
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- New method for promoting photosensitive oxidation to remove 1, 2-mercaptoethanol acetal protecting group by utilizing visible light irradiation
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The invention discloses a new method for removing a 1, 2-mercaptoethanol acetal protecting group, and belongs to the field of organic synthetic chemistry. The method comprises the following steps of:under a room-temperature open system, adding a substrate 2-substituted-1, 3-oxo-thio-cyclopentane and a catalytic amount of a photosensitizer Eosin Y into a proper amount of acetonitrile; and performing irradiating with a blue LED lamp for 3 hours while stirring to obtain the corresponding aldehyde compound with favorable yield. The method has the advantages of mild operation conditions, greenness, environmental protection, no harsh water and oxygen removal operation and device, realization of the reaction at room temperature, high substrate conversion rate, simple and easy post-treatment, andprovides a good method for removing the 1, 2-mercaptoethanol acetal protecting group at present.
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Paragraph 0014-0016
(2021/01/30)
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- Cerium-photocatalyzed aerobic oxidation of benzylic alcohols to aldehydes and ketones
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We have developed a cerium-photocatalyzed aerobic oxidation of primary and secondary benzylic alcohols to aldehydes and ketones using inexpensive CeCl3 7H2O as photocatalyst and air oxygen as the terminal oxidant.
- K?nig, Burkhard,Kumar, Sumit,Stahl, Jessica,Yatham, Veera Reddy,Yedase, Girish Suresh
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supporting information
p. 1727 - 1732
(2021/08/05)
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- Method for preparing aldehyde compounds by oxidative cleavage of carbon-carbon bonds of terminal alkene compounds
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The invention discloses a method for preparing aldehyde compounds by oxidizing and breaking carbon-carbon bonds of terminal alkene compounds. The method comprises the following steps: adding an alkene-terminated compound, an additive and a nitrogen-doped mesoporous carbon-loaded monatomic catalyst into a fatty primary alcohol solvent, putting into a pressure container, sealing, introducing oxygen source gas with a certain pressure, controlling the pressure of the oxygen source gas to be 0.1-1MPa and the reaction temperature to be 80-150 DEG C, and obtaining a reaction product, namely the aldehyde compound. The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention is high in activity, the highest separation yield of the aldehyde compound as a reaction product reaches 99%, the method is wide in application range, the reaction conditions are easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.
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Paragraph 0067-0068; 0089-0090
(2021/06/06)
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- Formation and Disproportionation of Xanthenols to Xanthenes and Xanthones and Their Use in Synthesis
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A facile and versatile strategy employing TiCl4-mediated cyclization followed by a Cannizzaro reaction has been developed for the synthesis of various xanthene derivatives. The reaction proceeded smoothly to afford both xanthenes/xanthones or their sulfur derivatives and tolerated a wide range of electronically diverse substrates. Using this methodology, pranoprofen was synthesized in three steps in 59% overall yield from commercially available starting materials.
- Shi, Zeyu,Chen, Si,Xiao, Qiong,Yin, Dali
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p. 3334 - 3343
(2021/02/05)
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- A metal-free radical cascade reaction of phosphine oxides with 2-aryloxy phenylacetylenes to synthesize diphosphonyl xanthene derivatives
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A radical cascade reaction of 2-aryloxy phenylacetylenes with phosphine oxides promoted by K2S2O8was developed, which provided diphosphonyl xanthenes as products. This reaction proceeds under transition metal-free and mild conditions with simple operation and good yields. The mechanistic study indicated that phosphine oxide was induced into a phosphonyl radical, and then the following double radical addition/cyclization with 2-aryloxy phenylacetylenes generated bisphosphonyl xanthenes.
- Chen, Yanyan,Fan, Tao,Jiang, Caina,Liu, Yan,Xu, Yanli
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supporting information
p. 6609 - 6612
(2021/08/10)
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- Lewis Acid Catalyzed Reductive Cyclization of 2-Aryloxybenzaldehydes and 2-(Arylthio)benzaldehydes to Unsubstituted 9H-Xanthenes and Thioxanthenes in Diisopropyl Ether
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Readily accessible 2-aryloxybenzaldehydes and 2-(arylthio)benzaldehydes undergo a sequence of reactions leading to a wide variety of unsubstituted 9H-xanthenes and thioxanthenes in high yields when heated with a Lewis acid in diisopropyl ether. This reductive cyclization method is compatible with several important functional groups. The method is also applicable for the selective reductive cyclization of the more electron-rich aryl ring of a 2,6-bis(aryloxy)benzaldehyde. The key feature of this transformation is the chemoselective reduction of a transient xanthylium ion in the presence of aldehydic group via intermolecular hydride transfer from diisopropyl ether (solvent). (Figure presented.).
- Verma, Shashi Kant,Prajapati, Anamika,Saini, Manoj Kumar,Basak, Ashok K.
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supporting information
p. 532 - 539
(2020/11/30)
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- Method for preparing diarylether compound
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The invention relates to a method for preparing a diarylether compound. The method comprises the following steps: dispersing an aromatic heterocyclic borate compound, a nitrobenzene compound, a coppercatalyst, an alkaline compound and an additive in an organic solvent, heating and stirring, and extracting, separating and purifying the obtained reaction solution by using an organic solvent after the reaction is completed to obtain the diarylether compound. Compared with the prior art, the method has the following advantages: the efficient preparation of the diarylether compound can be realizedunder the catalysis of bivalent copper with stable properties and low price; extra protection of inert gas is not needed, and the reaction is carried out under a heating condition in the air, so environmental friendliness is achieved; and expensive catalysis and ligands are not needed in the reaction, the reaction selectivity is high, the functional group tolerance of a substrate is good, the whole reaction process is simple and easy to implement, and the method is a brand-new synthesis method of the diarylether compound.
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Paragraph 0105-0113
(2020/06/02)
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- Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes
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An efficient visible light photoredox catalyzed aerobic deprotection of 1,3-oxathiolanes using organic dye Eosin Y as a photocatalyst is disclosed. The deprotection procedure features the use of a metal-free catalyst, mild conditions, a broad range of substrate scope, and good functional group tolerance. 35 examples were tested under the standard conditions and most of them afforded the deprotected products in modest to high yields.
- Yang, Mingyang,Xing, Zhimin,Fang, Bowen,Xie, Xingang,She, Xuegong
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supporting information
p. 288 - 291
(2020/01/13)
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- Catalysis with magnetically retrievable and recyclable nanoparticles layered with Pd(0) for C-C/C-O coupling in water
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Nanoparticles layered with palladium(0) were prepared from nano-sized magnetic Fe3O4 by coating it with silica and then reacting sequentially with phenylselenyl chloride under an N2 atmosphere and palladium(ii) chloride in water. The resulting Fe3O4?SiO2?SePh?Pd(0) NPs are magnetically retrievable and the first example of NPs in which the outermost layer of Pd(0) is mainly held by selenium. The weight percentage of Pd in the NPs was found to be 1.96 by ICP-AES. The NPs were authenticated via TEM, SEM-EDX, XPS, and powder XRD and found to be efficient as catalysts for the C-O and C-C (Suzuki-Miyaura) coupling reactions of ArBr/Cl in water. The oxidation state of Pd in the NPs having size distribution from ~12 to 18 nm was inferred as zero by XPS. They can be recycled more than seven times. The main features of the proposed protocols are their mild reaction conditions, simplicity, and efficiency as the catalyst can be separated easily from the reaction mixture by an external magnet and reused for a new reaction cycle. The optimum loading (in mol% of Pd) was found to be 0.1-1.0 and 0.01-1.0 for O-arylation and Suzuki-Miyaura coupling, respectively. For ArCl, the required amount of NPs was more as compared to that needed for ArBr. The nature of catalysis is largely heterogeneous.
- Joshi, Hemant,Sharma, Alpesh K.,Singh, Ajai K.
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p. 6452 - 6459
(2020/02/25)
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- Palladium complexes of chalcogenoethanamine (S/Se) bidentate ligands: Applications in catalytic arylation of C[sbnd]H and O[sbnd]H bonds
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This report describes the syntheses of N,E (E = S, Se) coordinated bidentate palladium complexes, by the reaction of N-(2-bromobenzyl)-2-(phenylthio/selanyl)ethanamine (3, 4) with [PdCl2(CH3CN)2]. The new ligands and palladium complexes were characterized by techniques like 1H, 13C{1H} NMR, IR, and elemental analysis. The coordination modes of ligand with palladium precursor in complexes 5 and 6 were authenticated by single crystal X-ray diffraction. The complexes possess distorted square planar geometry around palladium center. Thermally robust and air stable complexes 5 and 6 were used as catalyst for regioselective arylation of imidazole and O-arylation of phenol. In case of regioselective arylation of imidazole, the reaction proceeds smoothly under mild reaction conditions, only 2.0 mol% of catalyst loading is required to achieve high yield (76–92%). This protocol is applicable to a broad substrate scope showing excellent tolerance towards different functional groups. Whereas for O-arylation of phenol also only 2.0 mol% catalyst loading is sufficient to give good yield (71–92%) with excellent tolerance towards a broad range of functional groups. Among sulfur and selenium coordinated ligands, selenium ligand coordinated complex, was found to outperform the catalytic reactions in both cases as compare to sulfur ligand. The mercury and triphenylphosphine poisoning tests suggest homogeneous nature of catalysis.
- Bhatt, Ramprasad,Bhuvanesh, Nattamai,Himanshi,Joshi, Hemant,Sharma, Alpesh K.
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- Stereoselective synthesis of 9-vinyl substituted unsymmetrical xanthenes and thioxanthenes
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Activated 2°-allylic alcohols derived from 2-aryloxybenzaldehydes and 2-(arythio)benzaldehydes undergo intramolecular Friedel-Crafts alkylation reaction when heated with catalytic amount of a Lewis acid in 1,2-dichloroethane to provide highly E-selective 9-vinyl substituted unsymmetrical novel xanthenes and thioxanthenes in good yields.
- Prajapati, Anamika,Kumar, Mahendra,Thakuria, Ranjit,Basak, Ashok K.
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supporting information
(2020/08/19)
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- Optical Control of CRAC Channels Using Photoswitchable Azopyrazoles
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The Ca2+ release-activated Ca2+ (CRAC) channels control many Ca2+-modulated physiological processes in mammals. Hyperactivating CRAC channels are known to cause several human diseases, including Stormorken syndrome. Here, we show the design of azopyrazole-derived photoswitchable CRAC channel inhibitors (designated piCRACs), which enable optical inhibition of store-operated Ca2+ influx and downstream signaling. Moreover, piCRAC-1 has been applied in vivo to alleviate thrombocytopenia and hemorrhage in a zebrafish model of Stormorken syndrome in a light-dependent manner.
- Yang, Xingye,Ma, Guolin,Zheng, Sisi,Qin, Xiaojun,Li, Xiang,Du, Lupei,Wang, Youjun,Zhou, Yubin,Li, Minyong
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supporting information
p. 9460 - 9470
(2020/06/27)
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- Nickel-catalyzed denitrative etherification of activated nitrobenzenes
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Electron-deficient nitrobenzenes were coupled with phenols/alcohols to form diaryl/alkyl aryl ethers by the aid of NiCl2 as the catalyst. The reactions were conducted under ligand- and oxidant-free conditions without the exclusion of air or moisture. The initial studies upon the mechanism of the reaction revealed two solvent-dependent approaches. In molten TBAB, SNAr mechanism seems to be predominated, while, in DMF, the reaction might include the radical species.
- Zamiran, Fatemeh,Ghaderi, Arash
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p. 293 - 299
(2019/01/28)
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- In(OTf)3 catalyzed reductive etherification of 2-aryloxybenzaldehydes and 2-(arylthio)benzaldehydes
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2-Aryloxybenzaldehydes and 2-(arylthio)benzaldehydes undergo reductive etherification in presence of 5 mol% In(OTf)3 and stoichiometric amount of Et3SiH under solvent free conditions to generate novel symmetrical dibenzyl ethers and thioethers in excellent yields. In(OTf)3 is found to be superior in terms of catalytic activity over the other metal triflates tested for the reaction. Xanthenes and thioxanthenes, as anticipated, could not be obtained under these conditions.
- Prajapati, Anamika,Kumar, Mahendra,Thakuria, Ranjit,Basak, Ashok K.
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supporting information
(2019/10/02)
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- Pyrimidine onium compound and application thereof
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The invention relates to a pyrimidine onium compound, nitride oxides, salt of the nitride oxides and a composition comprising the compound. The invention further relates to an application of the compound to plant pest control.
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Paragraph 0171-0174
(2019/10/23)
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- Immobilized palladium nanoparticles on MNPs@A-N-AEB as an efficient catalyst for C-O bond formation in water as a green Solvent
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Palladium nanoparticles immobilized on the magnetic nanoparticles@2-amino-N-(2-aminoethyl) benzamide (MNPs@A-N-AEB.Pd0) have been presented as an efficient, and reusable magnetically heterogeneous catalyst for the C-O coupling reaction, namely Ullmann condensation reactions in an aqueous medium. This heterogeneous catalyst shows superior reactivity for the C-O arylation of different aryl halide (chloride, bromide, and iodide) with phenol derivatives to afford the desired products in good to excellent yields within short reaction time. Moreover, the catalyst can be easily recovered and reused for seven runs without loss of catalytic activity. The catalyst was characterized by several techniques, such as FT-IR, SEM, TEM, EDS, XRD, TGA and ICP-OES.
- Moghaddam, Firouz Matloubi,Eslami, Mohammad
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- Cyclic analogue of S-benzylisothiourea that suppresses kynurenine production without inhibiting indoleamine 2,3-dioxygenase activity
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Kynurenine is biosynthesised from tryptophan catalysed by indoleamine 2,3-dioxygenase (IDO). The abrogation of kynurenine production is considered a promising therapeutic target for immunological cancer treatment. In the course of our IDO inhibitor programme, formal cyclisation of the isothiourea moiety of the IDO inhibitor 1 afforded the 5-Cl-benzimidazole derivative 2b-6, which inhibited both recombinant human IDO (rhIDO) activity and cellular kynurenine production. Further derivatisation of 2b-6 provided the potent inhibitor of cellular kynurenine production 2i (IC50 = 0.34 μM), which unexpectedly exerted little effect on the enzymatic activity of rhIDO. Elucidation of the mechanism of action revealed that compound 2i suppresses IDO expression at the protein level by inhibiting STAT1 expression in IFN-γ-treated A431 cells. The kynurenine-production inhibitor 2i is expected to be a promising starting point for a novel approach to immunological cancer treatment.
- Fukuda, Miwa,Sasaki, Tomomi,Hashimoto, Tomoko,Miyachi, Hiroyuki,Waki, Minoru,Asai, Akira,Takikawa, Osamu,Ohno, Osamu,Matsuno, Kenji
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supporting information
p. 2846 - 2849
(2018/07/30)
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- NOVEL THIOUREA DERIVATIVES AS ACTIVATORS OF RORalpha AND PHARMACEUTICAL COMPOSITION CONTAINING SAME
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Provided is a compound activating RORα gene, particularly a JC1 compound containing CGP52608 thiazolidinedione as a lead substance, and a pharmaceutically acceptable salt thereof. The compound is a lipid accumulation inhibitor and applicable to the treatment of metabolic diseases or inflammatory diseases.
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Paragraph 0169
(2018/11/02)
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- Highly efficient heterogeneous copper-catalysed O-arylation of phenols by nitroarenes leading to diaryl ethers
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The heterogeneous O-arylation of phenols by nitroarenes was achieved in DMF at 100 °C by using an MCM-41-immobilised bidentate nitrogen copper(II) complex [MCM-41-2N-Cu(OAc)2] as catalyst, yielding a variety of unsymmetrical diaryl ethers in good to excellent yields. This heterogeneous copper catalyst can be easily prepared by a simple procedure from commercially readily available and inexpensive reagents, recovered by filtration of the reaction solution and recycled at least seven times without significant loss of activity.
- Du, Yingying,Yao, Fang,Tuo, Yuxin,Cai, Mingzhong
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p. 725 - 729
(2018/01/08)
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- Palladacycles of sulfated and selenated Schiff bases of ferrocene-carboxaldehyde as catalysts for O-arylation and Suzuki-Miyaura coupling
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Schiff base ligands (L1: sulfated and L2: selenated) having a ferrocene core synthesized by reacting ferrocene-carboxaldehyde with 2-(phenylthio/seleno)ethylamine on treatment with Na2PdCl4 in the presence of NaOAc give cyclopalladated complexes [Pd(L1/L2-H)Cl] (1/2). Complex 1 of a sulfated Schiff base L1, on reacting with one equivalent of triphenylphosphine gives complex [Pd(L1-H)PPh3Cl] (3), formed due to cleavage of a Pd-S bond. With 2 such a reaction does not occur, as a Pd-Se bond being stronger than that of its sulfur analogue does not get cleaved. L1, L2 and their complexes 1-3 were authenticated with HR-MS, 1H, 13C{1H} and 77Se{1H} NMR spectroscopy. The single crystal structures of 1-3 were determined with X-ray diffraction. Palladium in all three complexes has nearly a square planar geometry. The Pd-S, Pd-Se and Pd-P bond distances are 2.4249(12), 2.5058(14) and 2.2445(17) ? respectively. The catalytic activity of complexes 1-3 was explored for O-arylation of phenol and Suzuki-Miyaura coupling (SMC) of phenylboronic acid with aryl bromides and chlorides. The optimum reaction time for SMC of ArBr is 3 h whereas for ArCl it is 6 h. The TON values of O-arylation catalyzed with complexes 1-3 are up to ~170 (TOF, 28 h?1) and SMC ~9300 (TOF, 3100 h?1) for the reaction time of the order of 3 and 6 h respectively. The catalytic process is somewhat more efficient with 2 (Pd bonded with a selenoether group), than 3, followed by 1.
- Sharma, Alpesh K.,Joshi, Hemant,Bhaskar, Renu,Kumar, Satyendra,Singh, Ajai K.
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p. 2485 - 2496
(2017/03/08)
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- 1,3,8-TRIAZASPIRO[4,5]DECAN-4-ONE DERIVATIVES USEFUL FOR THE TREATMENT OF ORL-1 RECEPTOR MEDIATED DISORDERS
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The present invention is directed to novel 1,3,8-triazaspiro[4.5]decan-4-one derivatives of the general formulawherein all variables are as defined herein, useful in the treatment of disorders and conditions mediated by the ORL-1 G-protein coupled receptor. More particularly, the compounds of the present invention are useful in the treatment of disorders and conditions such as anxiety, depression, substance abuse, neuropathic pain, acute pain, migraine, asthma, cough and for improved cognition.
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Paragraph 0218-0220
(2017/02/28)
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- Tert -Butoxide mediated cascade desulfonylation/arylation/hydrolysis of cyclic sulfonyimines using diaryliodonium salts: Synthesis of diaryl ether derivatives bearing a 2-aldehyde group
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Cascades of cyclic sulfonyimines mediated by tBuOK with diaryliodonium salts has been developed, giving the diaryl ethers in good yields. Furthermore, bulky ortho-substituted diaryl ethers with an aldehyde group can be obtained easily in comparision with metal-catalyzed protocols.
- Qian, Xiaofei,Han, Jianwei,Wang, Limin
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p. 89234 - 89237
(2016/10/03)
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- PHARMACEUTICALLY ACTIVE COMPOUNDS AS DAG-LIPASE INHIBITORS
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The present invention relates to novel compounds which are highly selective inhibitors of diacylglycerol lipase α and β. These compounds are suitable for the treatment or prevention of disorders associated with, accompanied by or caused by increased 2-arachidonoylglycerol levels. Diacylglycerol lipase-α (alternative name: Sn1-specific diacylglycerol hydrolase a; DAGL-α) and -β are enzymes responsible for the biosynthesis of the endocannabinoid 2-arachidonoylglycerol. Selective and reversible inhibitors are required to study the function of DAGLs in neuronal cells in an acute and temporal fashion. The inventive ompounds are in particular suitable for the treatment of neurodegenerative diseases, inflammatory diseases, drug abuse and impaired energy balance, such as obesity.
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Paragraph 0110-0111
(2016/12/01)
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- Synthesis of targeted dibenzo[b,f]thiepines and dibenzo[b,f]oxepines as potential lead molecules with promising anti-breast cancer activity
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A targeted library of substituted dibenzo[b,f]thiepines and dibenzo[b,f]oxepines (prototypes I, II and III), and structurally analogous to tamoxifen have been synthesized as a new class of anti-breast cancer agents. All the prototype molecules exhibited potential antiproliferative activity against ER + ve and ER-ve breast cancer cell lines. Dibenzo[b,f]thiepine prototypes were found to be more active. Of all the compound tested, 14b exhibited potent in-vitro antiproliferative activity at 1.33 μM and 5 μM concentration in MCF-7 and MDA-MB-231 cell lines and was devoid of any cytotoxicity in normal HEK cells even at 50 μM. Cell cycle analysis showed that the compound 14b inhibited cell proliferation due to G0/G1 arrest in MCF-7 cells. Annexin-V FITC and PI staining experiments confirmed that the cell inhibition was primarily due to apoptosis and not by necrosis, which was also supported by LDH release assay experiment. Molecular docking studies showed better binding interaction of the new dibenzo[b,f]thiepine analogue 14b with the estrogen receptor (ER) as compared to 4-hydroxy-tamoxifen and this enhanced binding might be responsible for its estrogen antagonistic activity that induces cell cycle arrest, apoptosis and inhibition of breast cancer cells.
- Ansari, Mohd. Imran,Arun, Ashutosh,Chakravarti, Bandana,Hajela, K.,Hussain, Mohd. Kamil,Konwar, Rituraj
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p. 113 - 124
(2020/12/04)
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- Ruthenium-based metathesis catalysts, precursors for their preparation and their use
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The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost-effective manner. The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring-closing metathesis (RCM), cross metathesis (CM) and ring-opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.
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Paragraph 0075; 0078
(2014/05/20)
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- Metal-free synthesis of ortho -CHO diaryl ethers by a three-component sequential coupling
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A practical, metal-free, and highly chemoselective approach was developed for the synthesis of ortho-CHO diaryl ethers by a three-component sequential coupling of arynes, N,N-dimethylformamide (DMF), and diaryliodonium salts. Diverse functional groups including halo, nitryl, and bulky substituents and heteroaromatics are well tolerated. Mechanistically, isotopic tracer experiments reveal that the diaryliodonium salt serves as an electrophile to trap the transient intermediates generated from the [2 + 2] cyclization of an aryne and DMF.
- Liu, Fangliang,Yang, Huameng,Hu, Xinquan,Jiang, Gaoxi
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supporting information
p. 6408 - 6411
(2015/01/09)
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- O-arylation of iodophenols with 2-fluorobenzaldehyde under microwave conditions
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The arylation of 4-iodo-, 2-iodo- and 3-iodophenols with 2-fluorobenzaldehyde may be carried out in the presence of K2CO 3 in DMF as the solvent under microwave conditions. The arylation of 4-iodophenole was promoted by the use of triethylbenzylammonium chloride (TEBAC) as the phase transfer catalyst. In the other model reactions, the use of TEBAC was harmful. By-products formed by isomerization and disproportionation were also detected.
- Balint, Erika,Kallai, Monika,Kovacs, Orsolya,Boelcskei, Hedvig,Keglevich, Gyoergy
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p. 114 - 120
(2014/01/06)
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- Impregnated copper on magnetite as catalyst for the O-arylation of phenols with aryl halides
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Nanoparticle Fe3O4 encapsulated CuO, as a heterogeneous catalyst, is a facile system for the synthesis of diaryl ethers by the cross-coupling reaction of various substituted aryl halides with various substituted phenols, which avoids using any type of expensive ligand and can be recovered from the reaction mixture by using a simple magnet. Moreover, this catalyst can be reused three times with high catalytic activity.
- Zhang, Ying-Peng,Shi, Ai-Hong,Yang, Yun-Shang,Li, Chun-Lei
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p. 141 - 145
(2014/02/14)
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- RUTHENIUM-BASED METATHESIS CATALYSTS, PRECURSORS FOR THEIR PREPARATION AND THEIR USE
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The invention is directed to ruthenium-based metathesis catalysts of the Grubbs-Hoveyda type. The new 2-aryloxy-substituted ruthenium catalysts described herein reveal rapid initiation behavior. Further, the corresponding styrene-based precursor compounds are disclosed. The catalysts are prepared in a cross-metathesis reaction starting from styrene-based precursors which can be prepared in a cost- effective manner. The new Grubbs-Hoveyda type catalysts are suitable to catalyze ring- closing metathesis (RCM), cross metathesis (CM) and ring- opening metathesis polymerization (ROMP). Low catalyst loadings are necessary to convert a wide range of substrates including more complex and critical substrates via metathesis reactions at low to moderate temperatures in high yields within short reaction times.
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Page/Page column 23; 24
(2014/05/24)
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- First palladium-catalyzed denitrated coupling reaction of nitroarenes with phenols
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The first palladium-catalyzed protocol for the denitrated coupling reaction of nitroarenes with phenols has been developed, achieving unsymmetrical diaryl ethers in moderate to excellent yields. The cyclopalladated ferrocenylimine (catalyst Ic) exhibited highly catalytic activity for this transformation with low catalyst loading (0.75 mol%) and short reaction time (2 h). The efficiency of this reaction was demonstrated by its compatibility with a range of groups. Moreover, the rigorous exclusion of air or moisture was not required in these transformations. Copyright
- Wang, Hailei,Yu, Ajuan,Cao, Aijuan,Chang, Junbiao,Wu, Yangjie
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p. 611 - 614
(2013/10/21)
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- Graphene oxide grafted with Pd17Se15 nano-particles generated from a single source precursor as a recyclable and efficient catalyst for C-O coupling in O-arylation at room temperature
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The Pd17Se15 nanoparticles, synthesized for the first time from a single source precursor [Pd(L)Cl2] {L = 1,3-bis(phenylselenyl)propan-2-ol} and grafted onto graphene oxide, show high catalytic activity in C-O coupling between aryl/heteroaryl chlorides/bromides and phenol at room temperature (Pd loading 1 mol%; yield up to 94%).
- Joshi, Hemant,Sharma, Kamal Nayan,Sharma, Alpesh K.,Prakash, Om,Singh, Ajai Kumar
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supporting information
p. 7483 - 7485
(2013/08/23)
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- Design and synthesis of l- and d-phenylalanine derived rhodanines with novel C5-arylidenes as inhibitors of HCV NS5B polymerase
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Hepatitis C virus (HCV) NS5B polymerase is a key target for anti-HCV therapeutics development. Herein, we report the synthesis and in vitro evaluation of anti-NS5B polymerase activity of a molecular hybrid of our previously reported lead compounds 1 (IC50 = 7.7 μM) and 2 (IC50 = 10.6 μM) as represented by hybrid compound 27 (IC 50 = 6.7 μM). We have explored the optimal substituents on the terminal phenyl ring of the 3-phenoxybenzylidene moiety in 27, by generating a set of six analogs. This resulted in the identification of compound 34 with an IC50 of 2.6 μM. To probe the role of stereochemistry towards the observed biological activity, we synthesized and evaluated the d-isomers 41 (IC50 = 19.3 μM) and 45 (IC50 = 5.4 μM) as enantiomers of the l-isomers 27 and 34, respectively. The binding site of compounds 32 and 34 was mapped to palm pocket-I (PP-I) of NS5B. The docking models of 34 and 45 within the PP-I of NS5B were investigated to envisage the molecular mechanism of inhibition.
- Patel, Bhargav A.,Krishnan, Ramalingam,Khadtare, Nikhil,Gurukumar,Basu, Amartya,Arora, Payal,Bhatt, Aaditya,Patel, Maulik R.,Dana, Dibyendu,Kumar, Sanjai,Kaushik-Basu, Neerja,Talele, Tanaji T.
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p. 3262 - 3271
(2013/07/05)
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- Room temperature Ullmann type C-O and C-S cross coupling of aryl halides with phenol/thiophenol catalyzed by CuO nanoparticles
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C-O/C-S cross coupling of aryl halides with phenol or thiophenol was studied under ligand-free condition at room temperature over CuO nanocatalyst. The scope of the reaction was extended to various aryl halides and substituted phenols under optimized condition. In general, efficient, selective, and reusable heterogeneous nano CuO catalytic system has been developed for room temperature C-O and C-S Ullmann type cross coupling reactions.
- Babu, S. Ganesh,Karvembu
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p. 1677 - 1680
(2013/03/28)
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- Ligand-free catalytic system for the synthesis of diarylethers over Cu 2O/Cu-CNTs as heterogeneous reusable catalyst
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Various substituted diarylether derivatives were prepared by using heterogeneous reusable Cu2O- and Cu-coated carbon nanotubes (Cu 2O/Cu-CNTs) as catalyst under ligand-free conditions, which provided good to excellent yields. The catalyst was characterized by TEM, XRD, and AAS analysis. The effects of solvent, base, and amount of catalyst for the O-arylation were investigated. The catalyst could be recovered by simple filtration from the reaction mixture without further treatment and reused several times with consistent catalytic activity. In addition, CNTs could also be recovered from the used Cu2O/Cu-CNTs by a simple acid treatment.
- Zhang, Ying-Peng,Jiao, Ya-Cong,Yang, Yun-Shang,Li, Chun-Lei
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supporting information
p. 6494 - 6497
(2013/11/19)
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- Cross dehydrogenative coupling via base-promoted homolytic aromatic substitution (BHAS): Synthesis of fluorenones and xanthones
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Cross dehydrogenative coupling reactions occurring via base-promoted homolytic aromatic substitutions (BHASs) are reported. Fluorenones and xanthones are readily prepared via CDC starting with readily available ortho-formyl biphenyls and ortho-formyl biphenylethers, respectively. The commercially available and cheap tBuOOH is used as an oxidant. Initiation of the radical chain reaction is best achieved with small amounts of FeCp2 (0.1 or 1 mol %).
- Wertz, Sebastian,Leifert, Dirk,Studer, Armido
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supporting information
p. 928 - 931
(2013/03/28)
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- Metal-free oxidative coupling: Xanthone formation via direct annulation of 2-aryloxybenzaldehyde using tetrabutylammonium bromide as a promoter in aqueous medium
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A metal-free intramolecular annulation of 2-aryloxybenzaldehydes to xanthones is disclosed, which proceeds through the direct oxidative coupling of an aldehyde C-H bond and aromatic C-H bonds using tetrabutylammonium bromide (TBAB) as a promoter in aqueous medium. This strategy works smoothly in the presence of both electron-donating and electron-withdrawing groups, and displays good tolerance towards catalytically reactive substituents, thus promising further functionalizations of xanthone products.
- Rao, Honghua,Ma, Xinyi,Liu, Qianzi,Li, Zhongfeng,Cao, Shengli,Li, Chao-Jun
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supporting information
p. 2191 - 2196
(2013/10/01)
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- Fast olefin metathesis: Synthesis of 2-aryloxy-substituted Hoveyda-type complexes and application in ring-closing metathesis
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Four 1-(4-R-phenoxy)-2-ethenylbenzenes (R=NMe2, H, Cl, NO 2) 4a, 4b, 4c and 4d were reacted with the ruthenium complexes [RuCl2(NHC)(3-phenylindenylidene)(py)] in the presence of a protic resin to result in the formation of the respective Hoveyda-type complexes 5a-d {NHC=SIMes [1,3-bis(2,4,6-trimethylphenylimidazolin)-2-ylidene]} and 6a-d {NHC=SIPr [1,3-bis(2,6-diisopropylphenylimidazolin)-2-ylidene]} in 66-84% yield. The lower steric bulk and the decreased donation of the diaryl ether oxygen atoms in complexes 5 and 6 led to rapidly initiating precatalysts. The Ru(II/III) redox potentials of complexes 6 were determined (6a-d: ΔE=0.89-1.08 V). In the crystal structure of 5b two independent molecules were observed in the unit cell, displaying Ru-O distances of 226.6(4) and 230.5(3) pm. The catalytic performance of complexes 5 and 6 in various ring-closing metathesis (RCM) reactions was studied. Catalyst loadings of between 15-200 ppm are sufficient for the formation of >90% yield of the respective cyclic products. Complex 6b catalyzes the formation of N-protected 2,5-dihydropyrroles with up to TON 64,000 and TOF 256,000 h-1, of the N-protected 1,2,3,6- tetrahydropyridines with up to TON 18,200 and TOF 73,000 h-1 and of the N-protected 2,3,6,7-tetrahydroazepines with up to TON 8,100 and TOF 32,000 h-1 with yields ranging between 77 and 96%.
- Kos, Pavlo,Savka, Roman,Plenio, Herbert
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supporting information
p. 439 - 447
(2013/05/21)
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- Riccardin C derivatives as anti-MRSA agents: Structure-activity relationship of a series of hydroxylated bis(bibenzyl)s
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Members of a series of macrocyclic bis(bibenzyl) riccardin-class derivatives were found to exhibit antibacterial activity towards methicillin-resistant Staphylococcus aureus (anti-MRSA activity). Structure-activity relationship (SAR) studies were conducted, focusing on the number and position of the hydroxyl groups. The minimum essential structure for anti-MRSA activity was also investigated.
- Sawada, Hiromi,Okazaki, Miki,Morita, Daichi,Kuroda, Teruo,Matsuno, Kenji,Hashimoto, Yuichi,Miyachi, Hiroyuki
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p. 7444 - 7447
(2013/02/21)
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- Ligand-free copper-catalyzed O-arylation of nitroarenes with phenols
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The first example of ligand-free copper-catalyzed O-arylation of nitroarenes with phenols was developed, achieving unsymmetrical diaryl ethers in moderate to excellent yields. This arylation proceeded smoothly without promotion of the ligands, and displayed great functional group compatibility. Thus, the method represents a new, facile, and cost-effective approach to access unsymmetrical diaryl ethers.
- Chen, Jiuxi,Wang, Xingyong,Zheng, Xingwang,Ding, Jinchang,Liu, Miaochang,Wu, Huayue
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supporting information
p. 8905 - 8907
(2012/10/29)
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- Intramolecular 1,3-dipolar cycloaddition of nitrile N-oxide accompanied by dearomatization
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Intramolecular 1,3-dipolar cycloaddition of 2-phenoxybenzonitrile N-oxides to benzene rings, accompanied by dearomatization, formed the corresponding isoxazolines in high yields. The X-ray single-crystal structure analysis revealed that the reaction formed the cis-adduct as a single isomer. The substituents on the benzene rings markedly affected the reaction rate, yield, and structure of the final product.
- Yonekawa, Morio,Koyama, Yasuhito,Kuwata, Shigeki,Takata, Toshikazu
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supporting information; experimental part
p. 1164 - 1167
(2012/03/27)
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- The coupling of arylboronic acids with nitroarenes catalyzed by rhodium
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The coupling of arylboronic acids with electron-deficient nitroarenes was realized for the first time by using a rhodium(I) catalyst under an air atmosphere, achieving unsymmetrical diaryl ethers with yields ranging from poor to good. From a deuterium labeling experiment, the oxygen atom is derived from ambient water. The efficiency of this reaction was demonstrated by its compatibility with fluoro, bromo, chloro, and trifluoromethyl groups.
- Zheng, Xingwang,Ding, Jinchang,Chen, Jiuxi,Gao, Wenxiao,Liu, Miaochang,Wu, Huayue
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supporting information; experimental part
p. 1726 - 1729
(2011/05/06)
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- Fe3O4@mesoporouspolyaniline: A highly efficient and magnetically separable catalyst for cross-coupling of aryl chlorides and phenols
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A high surface, magnetic Fe3O4@mesoporouspolyaniline core-shell nanocomposite was synthesized from magnetic iron oxide (Fe 3O4) nanoparticles and mesoporouspolyaniline (mPANI). The novel porous magnetic Fe3O4 was obtained by solvothermal method under sealed pressure reactor at high temperature to achieve high surface area. The mesoporouspolyaniline shell was synthesized by in situ surface polymerization onto porous magnetic Fe3O4 in the presence of polyvinylpyrrolidone (PVP) and sodium dodecylbenzenesulfonate (SDBS), as a linker and structure-directing agent, through 'blackberry nanostructures' assembly. The material composition, stoichiometric ratio and reaction conditions play vital roles in the synthesis of these nanostructures as confirmed by variety of characterization techniques. The role of the mesoporouspolyaniline shell is to stabilize the porous magnetic Fe3O4 nanoparticles, and provide direct access to the core Fe3O4 nanoparticles. The catalytic activity of magnetic Fe3O 4@mesoporousPANI nanocomposite was evaluated in the cross-coupling of aryl chlorides and phenols. Copyright
- Arundhathi,Damodara,Likhar, Pravin R.,Kantam, M. Lakshmi,Saravanan,Magdaleno, Travis,Kwon, Sun Hee
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supporting information; experimental part
p. 1591 - 1600
(2011/08/03)
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- Rearrangement of 2-aryloxybenzaldehydes to 2-hydroxybenzophenones by rhodium-catalyzed cleavage of aryloxy C-O bonds
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Lost in the shuffle: An unprecedented rearrangement of the title compounds proceeds by the simultaneous rhodium-catalyzed cleavage of aryloxy C-O and aldehyde C-H bonds (see scheme). The reaction tolerates the presence of various catalytically reactive substituents such as aryl halides, nitrile, and esters.
- Rao, Honghua,Li, Chao-Jun
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supporting information; experimental part
p. 8936 - 8939
(2011/11/07)
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- Design, synthesis, and pharmacological evaluation of azetedine and pyrrolidine derivatives as dual norepinephrine reuptake inhibitors and 5-HT 1A partial agonists
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Compounds with combined norepinephrine reuptake inhibitor (NRI) and serotonin 1A (5-HT1A) partial agonist pharmacology may offer a new therapeutic approach for treating symptoms of neuropsychiatric disorders including ADHD, depression, and anxiety. Herein we describe the design and optimization of novel chemical matter that exhibits favorable dual NRI and 5-HT1A partial agonist activity. Lead compounds in this series were found to be devoid of activity at the dopamine transporter and were shown to be brain penetrant with high receptor occupancy.
- Pettersson, Martin,Campbell, Brian M.,Dounay, Amy B.,Gray, David L.,Xie, Longfei,O'Donnell, Christopher J.,Stratman, Nancy C.,Zoski, Kim,Drummond, Elena,Bora, Gary,Probert, Al,Whisman, Tammy
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scheme or table
p. 865 - 868
(2011/02/27)
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- A new synthesis of methyl 7 H-Dibenz[b,g]oxocin-6-carboxylates from Morita-Baylis-Hillman adducts of 2-phenoxybenzaldehydes
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A new synthetic method for methyl 7H-dibenz[b,g]oxocin-6-carboxylates by Friedel-Crafts reaction of readily available bromides of Morita-Baylis-Hillman adducts with aluminum chloride has been developed. Georg Thieme Verlag Stuttgart New York.
- Ahn, Sang-Hyun,Jang, Seung Soon,Han, Eun-Gu,Lee, Kee-Jung
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experimental part
p. 377 - 386
(2011/04/22)
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- Scandium triflate-catalyzed one-pot domino approach towards general and efficient syntheses of unsymmetrical 9-substituted xanthene derivatives
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A general and efficient one-pot cascade/tandem approach to synthesize unsymmetrical 9-aryl/heteroaryl xanthenes has been developed under extremely mild reaction conditions using 10 mol% Sc(OTf)3 as a catalyst. This strategy has been further extended to synthesize 9-(thioaryl) xanthenes through tandem carbon-sulfur (C-S) and carbon-carbon (C-C) bond formation. Novel C-C and C-S bond cleavage promoted by Sc(OTf)3 is also discussed during mechanistic investigation. The Royal Society of Chemistry.
- Singh, Ritesh,Panda, Gautam
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scheme or table
p. 1097 - 1105
(2010/06/15)
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- Efficient palladium-catalyzed coupling reactions of aryl bromides and chlorides with phenols
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A convenient and general palladium-catalyzed coupling reaction of aryl bromides and chlorides with phenols was developed. Various functional groups such as nitriles, aldehydes, ketones and esters are well tolerated and the corresponding products are obtained in good to excellent yield.
- Hu, Tongjie,Schulz, Thomas,Torborg, Christian,Chen, Xiaorong,Wang, Jun,Beller, Matthias,Huang, Jun
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supporting information; scheme or table
p. 7330 - 7332
(2010/06/14)
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- A new synthetic route to unsymmetrical 9-arylxanthenes
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A. facile and general three-step synthetic route towards unsymmetrical 9-arylxanthenes was developed. The reaction sequence involves nucleophilic substitution of commercially available 2-fluorobenzaldehydes with arenoxides, Grignard reaction of the resulting 2-arenoxybenzaldehydes with arylmagnesium bromides, followed by FeCl3-catalyzed intramolecular diarylmethylation of the resulting carbinols, This strategy was extended to access symmetrical as well as unsymmetrical 9-arylthioxanthenes.
- Das, Sajal Kumar,Singh, Ritesh,Panda, Gautam
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scheme or table
p. 4757 - 4761
(2010/02/28)
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- NOVEL PHENYL-ISOXAZOL-3-OL DERIVATIVE
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The present invention relates to a compound represented by formula (I), which has a GPR120 agonist action and thus is useful for treatment of diabetes mellitus or hyperlipidemia, or a pharmaceutically acceptable salt thereof. In the formula, (AA) represents a phenyl or the like, which may be substituted with a lower alkoxy group or the like; (BB) represents a divalent group or the like, derived by removal of two hydrogen atoms from a benzene which may be substituted with a halogen atom or the like; X represents a spacer having a main chain composed of 1-8 carbon atoms wherein 1-3 carbon atoms in the main chain may be substituted with an oxygen atom or the like; and Y represents a hydrogen atom or the like.
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Page/Page column 47
(2009/09/26)
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