- Synthesis of 9-ethoxycarbonyl-10(10aH)-oxo-5,6,7,8,8a,9-hexahydro-9,10a- anthracenecarbolactone and related compounds by manganese(III) mediated cyclization
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Novel tetracyclic lactone (5a), 9-ethoxycarbonyl-10(10aH)-oxo- 5,6,7,8,8a,9-hexahydro-9,10a-anthracenecarbolactone, was obtained in 34.8% yield by oxidative cyclization of diethyl trans-2-benzoylcyclohexylmalonate (4a) with manganese(III) acetate dihydrate in the presence of sodium acetate in acetic acid.
- Ohta, Shunsaku,Kajiura, Takahiro,Murai, Hiromichi,Yamashita, Masayuki,Kawasaki, Ikuo
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Read Online
- Kinetic Evidence for the Occurence of the Oxydianionic Tetrahedral Intermediates in the Hydrolyses of Methyl Salicylate and methyl o-Methoxybenzoate in Highly Alkaline Medium
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The kinetics of hydrolyses of methyl salicylate and methyl o-methoxybenzoate have been studied at various hydroxide ion concentrations ranging from 0.01 to 4.40 M for methyl salicylate and from 0.005 to 0.200 M formethyl o-methoxybenzoate at 35 deg C.The observed rate constants are independent of -> within the range 0.01-0.04 M and vary according to equation kobsd = A + B-> + C->2 within the range 0.04-3.60 M for hydrolysis of methyl salicylate where A = k3k1/(k1 + k3),B = k2k4/(k-2 + k4), and C = k2k5K/(k-2 + k4).The observed rate constants for hydrolysis of methyl o-methoxybenzoate follow the equation kobsd = B1-> + C1->2 where B1 = k1'k2'/(k-1' + k2') and C1 = k1'k3'K'/(k-1' + k2').The pH-independent observed rate constants are 1E4 and 1E5 times larger than the corresponding values for water-catalyzed cleavages of methyl benzoate and methyl o-methoxybenzoate, respectively.This rate enhancement has been attributed to the probable intramolecular general-base-catalyzed neutral hydrolysis of methyl salicylate.The ratios B/B1 and C/C1 have been found to be 0.0214 and 0.0004, respectively.The apperance of C and C1 terms in the kinetic equations has been attributed to the existence of the oxydianionic tetrahedral intermediates in the reaction mechanisms.The temperature dependence of hydrolysis of methyl salicylate has also been studied at two differentOH- concentrations.The intramolecular general-base-catalyzed rate enhancement has been found to be due toa favorable ΔS*.The hydrolytic cleavage of methyl salicylate has been found to be sensitive to the ionic strenght.The probable mechanisms for hydrolyses of both esters are considered.
- Khan, M. Niyaz,Olagbemiro, T. O.
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- Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate**
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A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.
- Pfennig, Victoria S.,Villella, Romina C.,Nikodemus, Julia,Bolm, Carsten
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supporting information
(2022/01/22)
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- Design, synthesis, and biological studies of novel 3-benzamidobenzoic acid derivatives as farnesoid X receptor partial agonist
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Farnesoid X receptor (FXR), a bile acid-activated nuclear receptor, regulates the metabolism of bile acid and lipids as well as maintains the stability of internal environment. FXR was considered as a therapeutic target of liver disorders, such as drug-induced liver injury, fatty liver and cholestasis. The previous reported FXR partial agonist 6 was a suitable lead compound in terms of its high potent and low molecular size, while the docking study of compound 6 suggested a large unoccupied hydrophobic pocket, which might be provided more possibility of structure-activity relationship (SAR) study. In this study, we have performed comprehensive SAR and molecular modeling studies based on lead compound 6. All of these efforts resulted in the identification of a novel series of FXR partial agonists. In this series, compound 41 revealed the best activity and strong interaction with binding pocket of FXR. Moreover, compound 41 protected mice against acetaminophen-induced hepatotoxicity by the regulation of FXR-related gene expression and improving antioxidant capacity. In summary, these results suggest that compound 41 is a promising FXR partial agonist suitable for further investigation.
- Hu, Lijun,Ren, Qiang,Deng, Liming,Zhou, Zongtao,Cai, Zongyu,Wang, Bin,Li, Zheng
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supporting information
(2020/12/25)
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- Synthesis and antioxidant activities of berberine 9-: O -benzoic acid derivatives
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Although berberine (BBR) shows antioxidant activity, its activity is limited. We synthesized 9-O-benzoic acid berberine derivatives, and their antioxidant activities were screened via ABTS, DPPH, HOSC and FRAP assays. The para-position was modified with halogen elements on the benzoic acid ring, which led to an enhanced antioxidant activity and the substituent on the ortho-position was found to be better than the meta-position. Compounds 8p, 8c, 8d, 8i, 8j, 8l, and especially 8p showed significantly higher antioxidant activities, which could be attributed to the electronic donating groups. All the berberine derivatives possessed proper lipophilicities. In conclusion, compound 8p is a promising antioxidant candidate with remarkable elevated antioxidant activity and moderate lipophilicity.
- Liu, Yanfei,Long, Shuo,Zhang, Shanshan,Tan, Yifu,Wang, Ting,Wu, Yuwei,Jiang, Ting,Liu, Xiaoqin,Peng, Dongming,Liu, Zhenbao
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p. 17611 - 17621
(2021/05/29)
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- Aerobic oxidation of aldehydes to carboxylic acids catalyzed by recyclable ag/c3 n4 catalyst
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The oxidation of aldehydes is an efficient methodology for the synthesis of carboxylic acids. Herein we hope to report a simple, efficient and recyclable protocol for aerobic oxidation of aldehydes to carboxylic acid by using C3N4 supported silver nanoparticles (Ag/C3N4) as a catalyst in aqueous solution under mild conditions. Under standard conditions, the corresponding carboxylic acids can be obtained in good to excellent yields. In addition, Ag/C3N4 is convenient for recovery and could be reused three times with satisfactory yields.
- Wu, Chaolong,Yao, Xiaoquan,Yu, Min,Zhou, Li,Zhu, Li
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p. 167 - 175
(2021/03/19)
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- Photo-induced deep aerobic oxidation of alkyl aromatics
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Oxidation is a major chemical process to produce oxygenated chemicals in both nature and the chemical industry. Presently, the industrial manufacture of benzoic acids and benzene polycarboxylic acids (BPCAs) is mainly based on the deep oxidation of polyalkyl benzene, which is somewhat suffering from environmental and economical disadvantage due to the formation of ozone-depleting MeBr and corrosion hazards of production equipment. In this report, photo-induced deep aerobic oxidation of (poly)alkyl benzene to benzene (poly)carboxylic acids was developed. CeCl3 was proved to be an efficient HAT (hydrogen atom transfer) catalyst in the presence of alcohol as both hydrogen and electron shuttle. Dioxygen (O2) was found as a sole terminal oxidant. In most cases, pure products were easily isolated by simple filtration, implying large-scale implementation advantages. The reaction provides an ideal protocol to produce valuable fine chemicals from naturally abundant petroleum feedstocks. [Figure not available: see fulltext.].
- Wang, Chang-Cheng,Zhang, Guo-Xiang,Zuo, Zhi-Wei,Zeng, Rong,Zhai, Dan-Dan,Liu, Feng,Shi, Zhang-Jie
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p. 1487 - 1492
(2021/07/10)
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- Efficiency of lithium cations in hydrolysis reactions of esters in aqueous tetrahydrofuran
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Lithium cations were observed to accelerate the hydrolysis of esters with hydroxides (KOH, NaOH, LiOH) in a water/tetrahydrofuran (THF) two-phase system. Yields in the hydrolysis of substituted benzoates and aliphatic esters using the various hydroxides were compared, and the effects of the addition of lithium salt were examined. Moreover, it was presumed that a certain amount of LiOH was dissolved in THF by the coordination of THF with lithium cation and hydrolyzed esters even in the THF layer, as in the reaction by a phase-transfer catalyst.
- Harada, Yumi,Hayashi, Kazuhiko,Ichimaru, Yoshimi,Imai, Masanori,Kojima, Yuki,Maeda, Azusa,Nakayama, Kanae,Sugiura, Kirara
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p. 581 - 594
(2021/06/06)
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- Alkali-modified heterogeneous Pd-catalyzed synthesis of acids, amides and esters from aryl halides using formic acid as the CO precursor
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To establish an environmentally friendly green chemical process, we minimized and resolved a significant proportion of waste and hazards associated with conventional organic acids and molecular gases, such as carbon monoxide (CO). Herein, we report a facile and milder reaction procedure, using low temperatures/pressures and shorter reaction time for the carboxyl- and carbonylation of diverse arrays of aryl halides over a newly developed cationic Lewis-acid promoted Pd/Co3O4catalyst. Furthermore, the reaction proceeded in the absence of acid co-catalysts, and anhydrides for CO release. Catalyst reusability was achievedviascalable, safer, and practical reactions that provided moderate to high yields, paving the way for developing a novel environmentally benign method for synthesizing carboxylic acids, amides, and esters.
- Fapojuwo, Dele Peter,Maqunga, Nomathamsanqa Prudence,Meijboom, Reinout,Mogudi, Batsile M.,Molokoane, Pule Petrus,Onisuru, Oluwatayo Racheal,Oseghale, Charles O.
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p. 26937 - 26948
(2021/08/17)
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- Platinum on carbon–catalyzed and chemoselective aqueous oxygen oxidation of aromatic acetals to benzoic acids
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Novel chemoselective transformations can diversify the synthetic pathways of the target molecules. The chemoselective oxidation of aromatic acetals to benzoic acid derivatives under platinum on carbon (Pt/C)–catalyzed oxygen oxidation conditions has been newly developed with a tolerance of aliphatic acetals and ketals. The present oxidation was clean and useful from the viewpoint of the easy removal of Pt/C and the use of molecular oxygen as a green oxidant in water as an abundant, non-toxic and environmentally friendly solvent.
- Yasukawa, Naoki,Matsuda, Takumi,Shimizu, Eisho,Sajiki, Hironao,Sawama, Yoshinari
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p. 145 - 152
(2020/01/28)
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- Preparation method of bimetallic catalyst oxidation aldehyde synthetic carboxylic acid (by machine translation)
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The method is, in a reaction solvent: under normal pressure oxygen condition, under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a bimetallic catalyst, at, DEG, under stirring . under a stirring condition with an aldehyde compound as a substrate 10-90 °C in a reaction solvent under, a stirring condition under the action of a bimetallic catalyst . The reaction solution is stirred, for. 1-12h, hours at; room temperature, under, the action, of a bimetallic 1:1 catalyst Cu(OAc) under the action of a bimetallic catalyst under the action of a bimetallic catalyst under the action of a double-metal catalyst. 2 · H2 O And Co(OAc)2 · 44H2 O As the bimetallic catalyst, can achieve the highest yield of the carboxylic acid product, in high yield, by adjusting the reaction temperature, solvent, catalyst amount, for different types of the raw material aldehyde 98%. (by machine translation)
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Paragraph 0018-0019
(2020/05/30)
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- Light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds
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Visible light-induced organic reactions are important chemical transformations in organic chemistry, and their efficiency highly depends on suitable photocatalysts. However, the commonly used photocatalysts are precious transition-metal complexes and elaborate organic dyes, which hamper large-scale production due to high cost. Here, for the first time, we report a novel strategy: light and oxygen-enabled sodium trifluoromethanesulfinate-mediated selective oxidation of C-H bonds, allowing high-value-added aromatic ketones and carboxylic acids to be easily prepared in high-to-excellent yields using readily available alkyl arenes, methyl arenes and aldehydes as materials. The mechanistic investigations showed that the treatment of inexpensive and readily available sodium trifluoromethanesulfinate with oxygen under irradiation of light could in situ form a pentacoordinate sulfide intermediate as an efficient photosensitizer. The method represents a highly efficient, economical and environmentally friendly strategy, and the light and oxygen-enabled sodium trifluoromethanesulfinate photocatalytic system represents a breakthrough in photochemistry. This journal is
- Fu, Hua,Liu, Can,Liu, Yong,Yang, Haijun,Zhu, Xianjin
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supporting information
p. 4357 - 4363
(2020/07/14)
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- Enhanced reactivity of twisted amides inside a molecular cage
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When an amide group is distorted from its planar conformation, the conjugation between the nitrogen lone pair and the π* orbital of the carbonyl is disrupted and the reactivity towards nucleophiles is enhanced. Although there are several reports on the synthesis of activated twisted amides, amide activation through mechanical twisting is much less common. Here, we report twisted amides that are stabilized through their inclusion in a self-assembled coordination cage. When secondary aromatic amides are included in a Td-symmetric cage, the cis-twisted conformation is favoured over the trans-planar one—as evidenced by single-crystal X-ray diffraction analysis—revealing that the amide can twist by up to 34°. As a consequence of this distortion, the hydrolysis of amides is significantly accelerated upon inclusion. [Figure not available: see fulltext.]
- Takezawa, Hiroki,Shitozawa, Kosuke,Fujita, Makoto
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p. 574 - 578
(2020/05/05)
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- Cp2TiCl2-Catalyzed Carboxylation of Aryl Chlorides with Carbon Dioxide in the Presence of n-BuMgCl
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Cp2TiCl2-catalyzed carboxylation of aryl chlorides with carbon dioxide to afford benzoic acids in good yields has been achieved in the presence of n-BuMgCl. The reaction proceeds by a sequential magnesium halide exchange reaction and carboxylation with CO2 in a wide variety of aryl chlorides under mild conditions.
- Hang, Wei,Yi, Yaping,Xi, Chanjuan
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supporting information
p. 1476 - 1479
(2020/01/21)
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- Palladium supported on a novel ordered mesoporous polypyrrole/carbon nanocomposite as a powerful heterogeneous catalyst for the aerobic oxidation of alcohols to carboxylic acids and ketones on water
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Preparation of an ordered mesoporous polypyrrole/carbon (PPy/OMC) composite has been described through a two-step nanocasting process using KIT-6 as a template. Characterization of the PPy/OMC nanocomposite by various analysis methods such as TEM, XRD, TGA, SEM and N2 sorption confirmed the preparation of a material with ordered mesoporous structure, uniform pore size distribution, high surface area and high stability. This nanocomposite was then used for the immobilization of palladium nanoparticles. The nanoparticles were almost uniformly distributed on the support with a narrow particle size of 20-25 nm, confirmed by various analysis methods. Performance of the Pd?PPy/OMC catalyst was evaluated in the aerobic oxidation of various primary and secondary alcohols on water as a green solvent, giving the corresponding carboxylic acids and ketones in high yields and excellent selectivity. The catalyst could also be reused for at least 10 reaction runs without losing its catalytic activity and selectivity. High catalytic efficiency of the catalyst can be attributed to a strong synergism between the PPy/OMC and that of supported Pd nanoparticles.
- Ganji, Nasim,Karimi, Babak,Najafvand-Derikvandi, Sepideh,Vali, Hojatollah
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p. 13616 - 13631
(2020/04/24)
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- A cyclometalated Ir(iii)-NHC complex as a recyclable catalyst for acceptorless dehydrogenation of alcohols to carboxylic acids
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In this work, we have synthesized two new [C, C] cyclometalated Ir(iii)-NHC complexes, [IrCp?(C∧C:NHC)Br](1a,b), [Cp? = pentamethylcyclopentadienyl; NHC = (2-flurobenzyl)-1-(4-methoxyphenyl)-1H-imidazoline-2-ylidene (a); (2-flurobenzyl)-1-(4-formylphenyl)-1H-imidazoline-2-ylidene (b)] via intramolecular C-H bond activation. The molecular structure of complex 1a was determined by X-ray single crystal analysis. The catalytic potentials of the complexes were explored for acceptorless dehydrogenation of alcohols to carboxylic acids with concomitant hydrogen gas evolution. Under similar experimental conditions, complex 1a was found to be slightly more efficient than complex 1b. Using 0.1 mol% of complex 1a, good-to-excellent yields of carboxylic acids/carboxylates have been obtained for a wide range of alcohols, both aliphatic and aromatic, including those involving heterocycles, in a short reaction time with a low loading of catalyst. Remarkably, our method can produce benzoic acid from benzyl alcohol on a gram scale with a catalyst-to-substrate ratio as low as 1?:?5000 and exhibit a TON of 4550. Furthermore, the catalyst could be recycled at least three times without losing its activity. A mechanism has been proposed based on controlled experiments and in situ NMR study.
- Borah, Dhrubajit,Das, Pankaj,Saha, Biswajit,Sarma, Bipul
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p. 16866 - 16876
(2020/12/18)
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- Cobalt-Catalyzed Reductive Carboxylation of Aryl Bromides with Carbon Dioxide
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Cobalt-catalyzed reductive carboxylation of aryl bromides with carbon dioxide has been developed. The reaction proceeded under one atm pressure of CO2 at 40 °C in the presence of cobalt iodide/2,2′-bipyridine catalysts and zinc dust as a reducing reagent. Various aryl bromides could be converted to the corresponding carboxylic acids in good to high yields. Preliminary mechanistic experiments ruled out intervention of intermediate organozinc species for carboxylation with CO2, thus suggesting a direct CO2 insertion into the corresponding ArCoBr species. (Figure presented.).
- Hang, Wei,Yi, Yaping,Xi, Chanjuan
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supporting information
p. 2337 - 2341
(2020/04/30)
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- Design, synthesis, and preliminary biological evaluation of 3′,4′,5′-trimethoxy flavonoid salicylate derivatives as potential anti-tumor agents
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According to the pharmacophore combination principle, a set of new 3′,4′,5′-trimethoxy flavonoid salicylate derivatives were designed, synthesized, and evaluated for biological activity. The cytotoxicity evaluation revealed that compound 10v exhibited higher potency than 5-Fu against HCT-116 cells. Preliminary biological activity studies showed that compound 10v could inhibit the colony formation and migration of HCT-116 cells. Besides, the Hoechst 33258 staining assay and flow cytometry revealed that treatment with compound 10v induced the apoptosis of HCT-116 cells in a concentration-dependent manner, while it had no effect on their cell cycle. The WB analysis suggested that HIF-1α, tubulin, HK-2, and PFK might be the potential pharmacophore targets of compound 10v. Tubulin was a potential drug target for compound 10v, which was explained by analyzing the crystal structure of compound 10v complexed with tubulin. These results indicated that compound 10v might be a promising anti-tumor agent candidate, deserving further optimization and evaluation.
- Deng, Xiangping,Liu, Renbo,Li, Junjian,Li, Zhongli,Liu, Juan,Xiong, Runde,Lei, Xiaoyong,Zheng, Xing,Xie, Zhizhong,Tang, Guotao
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p. 1874 - 1884
(2019/01/28)
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- Metal-free Synthesis of Spiro-2,2′-benzo[b]furan-3,3′-ones via PhI(OAc)2-Mediated Cascade Spirocyclization
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Treating the benzyl protected 3-hydroxy-1,3-bis(2-hydroxyphenyl)prop-2-en-1-ones solely with PhI(OAc)2 (PIDA) in DCE at room temperature readily furnished the seldom studied spiro-2,2′-benzo[b]furan-3,3′-ones in satisfactory to excellent yields. The hypervalent iodine reagent enables the metal-free cascade spirocyclization resulting in the dual oxidative C?O bond formation. (Figure presented.).
- Xing, Qingyu,Liang, Huiyuan,Bao, Mingmai,Li, Xuemin,Zhang, Jingran,Bi, Tianhao,Zhang, Yilin,Xu, Jun,Du, Yunfei,Zhao, Kang
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supporting information
p. 4669 - 4673
(2019/09/17)
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- Cr(VI) oxidation using cetylpicolinium dichromate: Kinetics of oxidation of benzaldehydes with a green protocol
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Oxidation kinetics of benzaldehyde and some of its ortho- and para-monosubstituted derivatives have been studied using cetylpicolinium dichromates, a class of novel phase transfer oxidants, in dichloromethane medium. The rate of reaction is first order with respect to oxidant and fractional order with respect to the substrates. The Michaelis–Menten type oxidation was observed with respect to the substrates. Benzaldehydes are found to be oxidized to their corresponding acids. The mechanism of oxidation reaction has been suggested based on the solvent isotope effect, Hammett plot, and thermodynamic study. The solvent isotope effect (kCHCl3/kCDCl3=?1.57) indicates the involvement of hydrogen exchange with the medium during oxidation reactions. A strong influence of specific solute–solvent interactions on the rate of the reaction is observed. Both the electron-withdrawing and electron-releasing substituents on the substrates accelerate the rate of reaction.
- Priyadarshini, Supriya,Dash, Sukalyan
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p. 105 - 111
(2018/11/27)
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- Nitrogen Dioxide Catalyzed Aerobic Oxidative Cleavage of C(OH)–C Bonds of Secondary Alcohols to Produce Acids
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Stable organic nitroxyl radicals are an important class of catalysts for oxidation reactions, but their wide applications are hindered by their steric hinderance, high cost, complex operation, and separation procedures. Herein, NO2 in DMSO is shown to effectively catalyze the aerobic oxidative cleavage of C(OH)?C bonds to form a carboxylic group, and NO2 was generated in situ by decomposition of nitrates. A diverse range of secondary alcohols were selectively converted into acids in excellent yields in this transition-metal-free system without any additives. Preliminary results also indicate its applicability to depolymerize recalcitrant macromolecular lignin. Detail studies revealed that NO2 from nitrates promoted the reaction, and NO2 served as hydrogen acceptor and radical initiator for the tandem oxidative reaction.
- Liu, Mingyang,Zhang, Zhanrong,Song, Jinliang,Liu, Shuaishuai,Liu, Huizhen,Han, Buxing
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supporting information
p. 17393 - 17398
(2019/11/11)
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- Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
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Reported is the synthesis of carboxylic acids, symmetrical ketones, and unsymmetrical ketones with selectivity achieved by exploiting the differential reactivity of sodium methyl carbonate with Grignard and organolithium reagents.
- Hurst, Timothy E.,Deichert, Julie A.,Kapeniak, Lucas,Lee, Roland,Harris, Jesse,Jessop, Philip G.,Snieckus, Victor
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supporting information
p. 3882 - 3885
(2019/06/07)
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- Metal-Free Aerobic Oxidative Selective C-C Bond Cleavage in Heteroaryl-Containing Primary and Secondary Alcohols
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A transition-metal-free aerobic oxidative selective C-C bond-cleavage reaction in primary and secondary heteroaryl alcohols is reported. This reaction was highly efficient and tolerated various heteroaryl alcohols, generating a carboxylic acid derivative and a neutral heteroaromatic compound. Experimental studies combined with density functional theory calculations revealed the mechanism underlying the selective C-C bond cleavage. This strategy also provides an alternative simple approach to carboxylation reaction.
- Xia, Anjie,Qi, Xueyu,Mao, Xin,Wu, Xiaoai,Yang, Xin,Zhang, Rong,Xiang, Zhiyu,Lian, Zhong,Chen, Yingchun,Yang, Shengyong
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- Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
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We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.
- Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
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supporting information
p. 3575 - 3580
(2019/04/14)
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- Palladium catalyzed hydrodefluorination of fluoro-(hetero)arenes
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Palladium catalyzed hydrodefluorination was developed for fine-tuning the properties of fluoro-(hetero)aromatic compounds. The robust reaction can be set up in air, requires only commercially available components, and tolerates a variety of heterocycles and functionalities relevant to drug discovery. Given the prevalence of fluorine incorporation around metabolic hotspots, the corresponding deuterodefluorination reaction may prove useful for converting fluorinated libraries to deuterated analogues to suppress the oxidative metabolism by kinetic isotope effects.
- Gair, Joseph J.,Grey, Ronald L.,Giroux, Simon,Brodney, Michael A.
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supporting information
p. 2482 - 2487
(2019/04/10)
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- Efficient Oxidation of Benzylic and Aliphatic Alcohols Using a Bioinspired Cross-Bridged Cyclam Manganese Complex with H2O2
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The cross-bridged cyclam manganese complex Mn(Me2EBC)Cl2 efficiently catalyzes the oxidation of benzylic and aliphatic alcohols at pH 3 in a mixture of acetonitrile and water at room temperature. The environmentally benign and high oxygen content oxidant H2O2 was adopted. Conversions of the alcohols to the corresponding carbonyl compounds reached 98 % with good to excellent selectivity. In addition, several lignin model compounds were also catalytically oxidized under these conditions, with excellent conversion (up to 96 %) and selectivity (up to 99 %).
- Zhang, Zhan,Khrouz, Lhoussain,Yin, Guochuan,Andrioletti, Bruno
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supporting information
p. 323 - 327
(2018/11/27)
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- Discovery, synthesis, biological evaluation and molecular docking study of (R)-5-methylmellein and its analogs as selective monoamine oxidase A inhibitors
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(R)-5-Methylmellein (5-MM), the major ingredient in the fermented mycelia of the medicinal fungus Xylaria nigripes (called Wuling Shen in Chinese)? was found to be a selective inhibitor against monoamine oxidase A (MAO-A) and might play an important role in the clinical usage of this edible fungus as an anti-depressive traditional Chinese medicine (TCM). Based on the discovery and hypothesis, a variety of (R)-5-MM analogs were synthesized and evaluated in vitro against two monoamine oxidase isoforms (MAO-A and MAO-B). Most synthetic analogs showed selective inhibition of MAO-A with IC50 values ranging from 0.06 to 29 μM, and compound 13aR is the most potent analog with high selectivity (IC50, MAO-A: 0.06 μM; MAO-B: >50 μM). Interestingly, the enzyme kinetics study of 13aR indicated that this ligand seemed to bind in the MAO-A active site according to so-called “tight-binding inhibition” mode. The molecular docking study of 13aR was thereafter performed in order to rationalize the obtained biological results.
- Huang, Chao,Xiong, Juan,Guan, Hui-Da,Wang, Chang-Hong,Lei, Xinsheng,Hu, Jin-Feng
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p. 2027 - 2040
(2019/04/10)
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- Dehydrogenation of Alcohols to Carboxylic Acid Catalyzed by in Situ-Generated Facial Ruthenium- CPP Complex
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A selective catalytic system for the dehydrogenation of primary alcohols to carboxylic acids using a facial ruthenium complex generated in situ from the [Ru(COD)Cl2]n and a hybrid N-heterocyclic carbene (NHC)-phosphine-phosphine ligand (CPP) has been first reported. The facial coordination model was unveiled by NMR analysis of the reaction mixture. Such a fac-ruthenium catalyst system exhibited high catalytic activity and stability, and a high turnover number of 20 000 could be achieved with catalyst loading as low as 0.002 mol %. The exceedingly high catalyst stability was tentatively attributed to both the anchoring role of NHC and the hemi-lability of phosphines. The catalytic system also features a wide substrate scope. In particular, the facial coordination of CPP ligands was found to be beneficial for sterically hindered alcohols, and ortho-substituted benzylic alcohols and bulky adamantanyl methanol as well as cholesterol were all found to be viable dehydrogenation substrates.
- Liu, Hui-Min,Jian, Lei,Li, Chao,Zhang, Chun-Chun,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua,Li, Rui-Xiang
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p. 9151 - 9160
(2019/08/12)
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- Palladium complex containing diphosphine m-carborane ligand as well as preparation and application of palladium complex
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The invention relates to a palladium complex containing a diphosphine m-carborane ligand as well as a preparation and an application of the palladium complex. The preparation method of the palladium complex comprises the following steps of 1) adding an n-BuLi solution into a m-carborane solution, and then reacting for 30-60 minutes at a room temperature; 2) adding diphenyl phosphorus chloride, andreacting for 3-6 h at the room temperature; and 3) adding PdCl2, reacting at the room temperature for 3-5 hours, and carrying out post-treatment to obtain the palladium complex. The palladium complexis used for catalyzing the reaction of halohydrocarbon with carbon dioxide to synthesize carboxylic acid. Compared with the prior art, the synthesis process is simple and green, and has the excellentselectivity and high yield; the palladium complex has the stable physicochemical properties and is used as the catalyst, the halogenated hydrocarbon is used as a substrate, the palladium complex andthe halogenated hydrocarbon are jointly dissolved in toluene, and the carbon dioxide is introduced at the normal pressure for reaction, so that the corresponding carboxylic acid can be synthesized athigh yield.
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Paragraph 0067-0070
(2019/12/02)
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- CO2 activation by electrogenerated divalent samarium for aryl halide carboxylation
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The reductive carboxylation of aryl halides has been investigated using a samarium electrode as a sacrificial anode to yield the corresponding benzoic acids, providing a smooth strategy for CO2 activation. Carboxylation occurred after an efficient reduction of carbon dioxide mediated by an electrogenerated Sm(ii)-complex acting as a strong monoelectronic reductive reagent.
- Bazzi, Sakna,Le Duc, Ga?tan,Schulz, Emmanuelle,Gosmini, Corinne,Mellah, Mohamed
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supporting information
p. 8546 - 8550
(2019/10/02)
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- A mild method for synthesizing carboxylic acids by oxidation of aldoximes using hypervalent iodine reagents
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A mild oxidation method for the conversion of aldoximes to carboxylic acids was developed mediated by hypervalent iodine reagents. This method covers a wide range of functionalized aldoximes and proceeds under mild conditions, utilizing PhI(OH)OTs as an oxidant.
- Nakamura, Akira,Kanou, Hodaka,Tanaka, Junki,Imamiya, Akira,Maegawa, Tomohiro,Miki, Yasuyoshi
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supporting information
p. 541 - 544
(2018/02/07)
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- Unusual synthesis of azines and their oxidative degradation to carboxylic acid using iodobenzene diacetate
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Reaction of 3-hydrazonobutan-2-one oxime with aromatic aldehydes resulted in the formation of 1,2-bis(arylidene)hydrazine commonly referred as azine as an unexpected product, instead of expected product 3-(aryl)methylenehydrazonobutan-2-one oxime, which were subsequently oxidized to corresponding aromatic acids with an ecofriendly oxidizing agent iodobenzene diacetate. Azines and carboxylic acids were characterized by IR and NMR (1H, 13C, HMBC, and HMQC) studies.
- Sumran, Garima,Aggarwal, Ranjana,Hooda, Mona,Sanz, Dionisia,Claramunt, Rosa M.
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supporting information
p. 439 - 446
(2018/02/06)
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- A Highly Efficient NHC-Catalyzed Aerobic Oxidation of Aldehydes to Carboxylic Acids
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An N-heterocyclic carbene (NHC) organocatalytic aerobic oxidation of aldehydes to the corresponding carboxylic acids is explored. Remarkably, this method allows for efficient conversion of different classes of aldehydes including highly challenging electron-rich aryl aldehydes, ortho -substituted aryl aldehydes, various heteroaromatic aldehydes and α,β-unsaturated aldehydes under mild reaction conditions. These substrates, under previously reported NHC-catalyzed methods, are typically unreactive or give poor yields, require high reaction temperatures and reaction times of several days.
- Khatana, Anil Kumar,Singh, Vikram,Gupta, Manoj Kumar,Tiwari, Bhoopendra
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p. 4290 - 4294
(2018/11/23)
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- Transition-metal-free conversion of lignin model compounds to high-value aromatics: Scope and chemoselectivity
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An efficient and straightforward reaction protocol for the conversion of lignin model compounds was developed based on a simple system consisting of a base, oxygen, and a green solvent under mild conditions in the absence of metals. This protocol was successfully applied to the cleavage of both 'β-O-4' dimeric and trimeric compounds, and a controlled selective degradation was achieved depending on the bond type. The feasibility of this method to provide aromatic compounds in high yields from lignin by a sequential oxidative dehomologation reaction was clearly demonstrated.
- Lee, Tae Woo,Yang, Jung Woon
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p. 3761 - 3771
(2018/08/21)
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- A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids
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Herein, we present a study on the oxidation of aldehydes to carboxylic acids using three recombinant aldehyde dehydrogenases (ALDHs). The ALDHs were used in purified form with a nicotinamide oxidase (NOx), which recycles the catalytic NAD+ at the expense of dioxygen (air at atmospheric pressure). The reaction was studied also with lyophilised whole cell as well as resting cell biocatalysts for more convenient practical application. The optimised biocatalytic oxidation runs in phosphate buffer at pH 8.5 and at 40 °C. From a set of sixty-one aliphatic, aryl-Aliphatic, benzylic, hetero-Aromatic and bicyclic aldehydes, fifty were converted with elevated yield (up to >99%). The exceptions were a few ortho-substituted benzaldehydes, bicyclic heteroaromatic aldehydes and 2-phenylpropanal. In all cases, the expected carboxylic acid was shown to be the only product (>99% chemoselectivity). Other oxidisable functionalities within the same molecule (e.g. hydroxyl, alkene, and heteroaromatic nitrogen or sulphur atoms) remained untouched. The reaction was scaled for the oxidation of 5-(hydroxymethyl)furfural (2 g), a bio-based starting material, to afford 5-(hydroxymethyl)furoic acid in 61% isolated yield. The new biocatalytic method avoids the use of toxic or unsafe oxidants, strong acids or bases, or undesired solvents. It shows applicability across a wide range of substrates, and retains perfect chemoselectivity. Alternative oxidisable groups were not converted, and other classical side-reactions (e.g. halogenation of unsaturated functionalities, Dakin-Type oxidation) did not occur. In comparison to other established enzymatic methods such as the use of oxidases (where the concomitant oxidation of alcohols and aldehydes is common), ALDHs offer greatly improved selectivity.
- Knaus, Tanja,Tseliou, Vasilis,Humphreys, Luke D.,Scrutton, Nigel S.,Mutti, Francesco G.
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supporting information
p. 3931 - 3943
(2018/09/11)
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- Studies on Iron-Catalyzed Aerobic Oxidation of Benzylic Alcohols to Carboxylic Acids
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A comprehensive study on aerobic oxidation of benzylic alcohols to carboxylic acids with a catalytic amount each of Fe(NO 3) 3 ·9H 2 O, TEMPO, and KCl is conducted. Various synthetically useful functional groups are well tolerated in the reaction. Distinct electronic and steric effects are observed in the reaction: electron-withdrawing groups accelerate the reaction while electron-donating groups make the reaction slower, and ortho -substituted substrates react slower than meta -substituted substrates. Several large-scale reactions (100 mmol) are conducted using a slow air flow of 30 mL/min to demonstrate the practicality of this method in an academic laboratory.
- Jiang, Xingguo,Ma, Shengming
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p. 1629 - 1639
(2018/02/26)
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- Facile oxidation of alcohols to carboxylic acids in basic water medium by employing ruthenium picolinate cluster as an efficient catalyst
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Selective transformation of alcohols into carboxylic acids is a crucial process in industry for the synthesis of bulk chemicals. Current methods for the production of acids involve oxygen under pressure or toxic reagents like ruthenium chlorite or iodate or chromium oxides. Herein, we report the preparation of [Ru3(CO)8(C5H4NCO2)2] cluster which is an efficient catalyst precursor for the conversion of primary alcohols into carboxylic acids under aerobic conditions. The catalytic process involves the use of NaOH in a water–isopropanol medium which gives a 90% yield of carboxylic acid (90% yield for benzoic acid in standard reaction). This clean process appears to be safe for the synthesis of various benzoic acids for both laboratory and also industrial purposes.
- Singh, Ajeet,Singh, Sandip K.,Saini, Anoop K.,Mobin, Shaikh M.,Mathur, Pradeep
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- A cyclotrimethoxone-substituted salicylate compound and anti-tumor effect thereof
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The invention relates to the technical field of medicines, and designs and synthesizes a novel A cyclotrimethoxy 4'-hydroxyflavone compound and an A cyclotrimethoxone-substituted salicylate compound. The figure 1 is a general formula of the A cyclotrimethoxone-substituted salicylate compound, wherein in the formula, R1, R2 and R3 are equal to OCH3 or R2, R3 and R4 are equal to OCH3; R5- is equal to OCH3, CH3, F, Cl, Br, I or the like. The novel A cyclotrimethoxy 4'-hydroxyflavone compound and the A cyclotrimethoxone-substituted salicylate compound can have an obvious inhibiting effect on MGC-803 (human gastric carcinoma cells), HepG2 (human hepatoma carcinoma cells), MCF-7 (human breast cancer cells) and hopefully become anti-tumor drugs. The invention discloses a preparation method of the novel A cyclotrimethoxy 4'-hydroxyflavone compound and the A cyclotrimethoxone-substituted salicylate compound.
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-
Paragraph 0024; 0025
(2017/07/19)
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- Design, synthesis and biological evaluation of flavonoid salicylate derivatives as potential anti-tumor agents
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A series of flavonoid salicylate derivatives containing trimethoxybenzene and a series of chrysin salicylate derivatives were synthesized for use as anti-tumor agents, and evaluated for antiproliferative activity using three human tumor cells: MCF-7 (breast carcinoma cells), HepG2 (liver carcinoma cells), MGC-803 (gastric carcinoma cells) and the mice tumor cells MFC (forestomach carcinoma cells). A substituent group of a suitable size and the trimethoxybenzene had a certain influence on the bioactivity of the flavonoid salicylate derivatives. Compound 2 and its salicylate derivatives 7a-7g containing the trimethoxybenzene exhibited more antiproliferative activity. Among them, compound 7g displayed the most potent antiproliferative activity against MGC-803 cells and MFC cells with the concentration causing 50% inhibition of cell growth (IC50) values of 11.05 ± 1.58 μM and 13.73 ± 2.04 μM, respectively. The flow cytometry results showed that compound 7g caused the cell cycle to be arrested in the G0/G1 phase and induced apoptosis of MFC cells in a dose-dependent manner. Furthermore, compound 7g showed good anti-tumor activity in vivo. These results suggested that compound 7g could be a new, potent anti-tumor candidate which should be optimized and evaluated further.
- Deng, Xiangping,Wang, Zhe,Liu, Juan,Xiong, Shujuan,Xiong, Runde,Cao, Xuan,Chen, Yanming,Zheng, Xing,Tang, Guotao
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p. 38171 - 38178
(2017/08/16)
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- SO2F2-Mediated One-Pot Synthesis of Aryl Carboxylic Acids and Esters from Phenols through a Pd-Catalyzed Insertion of Carbon Monoxide
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A one-pot Pd-catalyzed carbonylation of phenols into their corresponding aryl carboxylic acids and esters through the insertion of carbon monoxide has been developed. This procedure offers a direct synthesis of aryl carboxylic acids and esters from inexpensive and abundant starting materials (phenols, SO2F2 and CO) under mild conditions. This method tolerates a broad range of functional groups and is also applicable for the modification of complicated natural products.
- Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
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p. 2323 - 2331
(2017/09/06)
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- Oxalic acid as the: In situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides
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An efficient palladium-catalyzed hydroxycarbonylation reaction of arylhalides using oxalic acid as a CO source has been developed. The reaction features high safety, low catalyst loading, and a broad substrate scope, and provides a safe and tractable approach to access a variety of aromatic carboxylic acid compounds. Mechanistic studies revealed the decomposition pattern of oxalic acid.
- Shao, Changdong,Lu, Ailan,Wang, Xiaoling,Zhou, Bo,Guan, Xiaohong,Zhang, Yanghui
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supporting information
p. 5033 - 5040
(2017/07/10)
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- Benzene C-H Etherification via Photocatalytic Hydrogen-Evolution Cross-Coupling Reaction
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Aryl ethers can be constructed from the direct coupling between the benzene C-H bond and the alcohol O-H bond with the evolution of hydrogen via the synergistic merger of photocatalysis and cobalt catalysis. Utilizing the dual catalyst system consisting of 3-cyano-1-methylquinolinum photocatalyst and cobaloxime, intermolecular etherification of arenes with various alcohols and intramolecular alkoxylation of 3-phenylpropanols with formation of chromanes are accomplished. These reactions proceed at remarkably mild conditions, and the sole byproduct is equivalent hydrogen gas.
- Zheng, Yi-Wen,Ye, Pan,Chen, Bin,Meng, Qing-Yuan,Feng, Ke,Wang, Wenguang,Wu, Li-Zhu,Tung, Chen-Ho
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supporting information
p. 2206 - 2209
(2017/05/12)
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- Conformations, equilibrium thermodynamics and rotational barriers of secondary thiobenzanilides
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The article deals with conformational behaviour of 2-methoxy-2′-hydroxythiobenzanilides. The CS-NH group of these compounds preferentially adopts the Z-conformation. Entropy favours the Z-conformer over the E-conformer, whereas enthalpy slightly favours the E-conformer over the Z-conformer. The rotational barrier about the CS-NH bond was determined to be (81.5±0.4) kJ/mol. No significant rotational barrier was found on the Ar-CS and Ar-NH bonds. All experimental outcomes are compared with the results of quantum-chemical calculations.
- Kozic, Ján,Novák, Zdeněk,?ímal, Václav,Profant, Václav,Kune?, Ji?í,Vin?ová, Jarmila
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p. 2072 - 2083
(2016/04/09)
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- A methoxylphenylboronic preparation of formic acid method
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The invention discloses a preparation method of alkali metal methoxybenzoate shown in a formula B. The preparation method comprises the following steps: 1, under the protection of inert gas, performing nucleophilic substitution reaction on a compound A and sodium methylate in methanol, wherein the reaction temperature is 80-150 DEG C and the reaction pressure is 0.18-1.4 MPa; 2, directly mixing a solution obtained in the step 1 with alkali metal hydroxide and water, removing methanol, and performing hydrolysis reaction to obtain a compound B, wherein the reaction temperature is 90-190 DEG C, and alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide; performing acidification reaction on the prepared compound B and acid to prepare methoxybenzoic acid shown in a formula C. According to the method, the raw materials are easily available, a low-price safe reagent is used, and a one-pot process is adopted; the method is low in alkali consumption, little in environmental pollution, easy to perform, high in yield and suitable for industrialized production.
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Paragraph 0040-0045
(2020/02/08)
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- * One derivative containing nitrogen and its preparation method and application (by machine translation)
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The invention discloses a formula (I) of formula (II) containing nitrogen mouth Shan Tong derivative and its preparation method and application, A new synthesis of this invention containing nitrogen mouth Shan Tong derivatives of the salt and its acid salt, increased solubility, active research indicates part of the compound at the same time with treating and/or preventing diabetes and complications from diabetes mellitus the role of the, can further carry out development research as a model for treating and/or preventing diabetes caused by the complications of diabetes medicine. (by machine translation)
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Paragraph 0091-0092
(2017/01/31)
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- Iodine-catalyzed oxidative C-C bond cleavage for benzoic acids and benzamides from alkyl aryl ketones
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Iodine-catalyzed oxidative C-C bond cleavage has been performed for the facile synthesis of both benzoic acids and benzamides from readily available alkyl aryl ketones. Additionally benzylidene acetones and phenylacetylenes were also converted to the corresponding aromatic acids under the same conditions. This approach features the use of inexpensive iodine as a catalyst, broad substrate scope and open air conditions.
- Sathyanarayana, Pochampalli,Upare, Atul,Ravi, Owk,Muktapuram, Prathap Reddy,Bathula, Surendar Reddy
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p. 22749 - 22753
(2016/03/15)
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- Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water
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The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification.
- Liu, Mingxin,Li, Chao-Jun
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supporting information
p. 10806 - 10810
(2016/09/03)
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- Chemoselective Transformation of Diarylethanones to Arylmethanoic Acids and Diarylmethanones and Mechanistic Insights
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The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, 1H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials.
- Wang, Xing,Chen, Rui-Xi,Wei, Zeng-Feng,Zhang, Chen-Yang,Tu, Hai-Yang,Zhang, Ai-Dong
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p. 238 - 249
(2016/01/15)
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- Flow carbonylation of sterically hindered ortho-substituted iodoarenes
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The flow synthesis of ortho-substituted carboxylic acids, using carbon monoxide gas, has been studied for a number of substrates. The optimised conditions make use of a simple catalyst system compromising of triphenylphosphine as the ligand and palladium acetate as the pre-catalyst. Carbon monoxide was introduced via a reverse "tube-in-tube" flow reactor at elevated pressures to give yields of carboxylated products that are much higher than those obtained under normal batch conditions.
- Mallia, Carl J.,Walter, Gary C.,Baxendale, Ian R.
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supporting information
p. 1503 - 1511
(2016/08/02)
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- Bridging C?H Activation: Mild and Versatile Cleavage of the 8-Aminoquinoline Directing Group
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8-Aminoquinoline has emerged as one of the most powerful bidentate directing groups in history of C?H activation within the last decade. However, cleavage of its robust amide bond has shown to be challenging in several cases, thus jeopardizing the general synthetic utility of the method. To overcome this limitation, we herein report a simple oxidative deprotection protocol. This transformation rapidly converts the robust amide to a labile imide, allowing subsequent cleavage in a simple one-pot fashion to rapidly access carboxylic acids or amides as final products.
- Berger, Martin,Chauhan, Rajan,Rodrigues, Catarina A. B.,Maulide, Nuno
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supporting information
p. 16805 - 16808
(2016/11/16)
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- An Aerobic Alternative to Oxidative Ozonolysis of Styrenes
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A general, selective and extremely efficient procedure for the aerobic cleavage of aromatic alkenes is presented. TON values in the range 6,000,000-10,000,000 are obtained for this nickel-catalyzed reaction performed in polyethylene glycol 400 under 1 atm of molecular oxygen. Mono-, di-, tri- and tetrasubstituted styrene derivatives are oxidatively cleaved by this reproducible protocol, also suitable for larger scale (1.5 g) reactions. The presence of several functional groups (alkyl, alkoxy, halogen, trifluoromethyl) is tolerated in the substrates. The mechanistic proposal to explain the selective generation of carboxylic acids and ketones from aromatic alkenes involves the participation of the polyol solvent in the presented oxidative process.
- Urgoitia, Garazi,Sanmartin, Raul,Herrero, María Teresa,Domínguez, Esther
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supporting information
p. 1150 - 1156
(2016/04/09)
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