- In vitro liver metabolism of aclidinium bromide in preclinical animal species and humans: Identification of the human enzymes involved in its oxidative metabolism
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The metabolism of aclidinium bromide, a novel long-acting antimuscarinic drug for the maintenance treatment of chronic obstructive pulmonary disorder, has been investigated in liver microsomes and hepatocytes of mice, rats, rabbits, dogs, and humans. Due to the rapid hydrolysis of this ester compound, two distinct radiolabeled forms of aclidinium were studied. The main biotransformation route of aclidinium was the hydrolytic cleavage of the ester moiety, resulting in the formation of the alcohol metabolite (M2, LAS34823) and carboxylic acid metabolite (m3, LAS34850), which mainly occurred non-enzymatically. By comparison, the oxidative metabolism was substantially lower and the metabolite profiles were similar across all five species examined. Aclidinium was metabolized oxidatively to four minor primary metabolites that were identified as monohydroxylated derivatives of aclidinium at the phenyl (M4) and glycolyl (m6 and m7) moieties of the molecule. The NADPH-dependent metabolite m4 involved the loss of one of the thiophene rings of aclidinium. Incubations with human recombinant P450 isoforms and inhibition studies with selective chemical inhibitors and antibodies of human P450 enzymes demonstrated that the oxidative metabolism of aclidinium is primarily mediated by CYP3A4 and CYP2D6. Additionally, up to eight secondary metabolites were also characterized, involving further hydrolysis, oxidation, or glucuronidation of the primary metabolites. Also, the liver oxidative metabolism of the alcohol metabolite (LAS34823) resulted in the production of one hydroxylated metabolite (M1) mediated by human CYP2D6, whereas the acid metabolite (LAS34850) was not metabolized enzymatically, although a minor non-enzymatic and NADPH-dependent reduction was observed.
- Albertí, Joan J.,Sentellas, Sònia,Salvà, Miquel
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Read Online
- Synthesis of α-Keto Acids via Oxidation of Alkenes Catalyzed by a Bifunctional Iron Nanocomposite
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An efficient methodology for synthesis of α-keto acids via oxidation of alkenes using TBHP as oxidant catalyzed by a bifunctional iron nanocomposite has been established. A variety of alkenes with different functional groups were smoothly oxidized into their corresponding α-keto acids in up to 80% yield. Moreover, the bifunctional iron nanocomposite catalyst showed outstanding catalytic stability for successive recycles without appreciable loss of activity.
- Song, Tao,Ma, Zhiming,Wang, Xiaoxue,Yang, Yong
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supporting information
p. 5917 - 5921
(2021/07/31)
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- Novel peptidomimetic peptide deformylase (PDF) inhibitors of Mycobacterium tuberculosis
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Emergence of MDR-TB and XDR-TB led to the failure of available anti-tubercular drugs. In order to explore, identify and develop new anti-tubercular drugs, novel peptidomimetic series of Mtb–peptide deformylase (PDF) inhibitors was designed and synthesized. In vitro antimycobacterial potential of compounds was established by screening of compounds against Mycobacterium tuberculosis H37Rv strain using MABA. Among them, ester series of compounds 4a, 4b, 4c, 4d, and 4e were found most active, with compound 4c being highly active and exhibiting minimum inhibitory concentration of 6.25?μg/ml against M.?tb H37Rv strain. Additionally, the compounds were docked to determine the probable binding interactions and understand the mechanism of action of most active molecules on Mtb-peptide deformylase (PDF), which is involved in the mycobacterium protein synthesis.
- Gokhale, Kunal M.,Telvekar, Vikas N.
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p. 148 - 156
(2020/08/26)
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- Possible competitive modes of decarboxylation in the annulation reactions ofortho-substituted anilines and arylglyoxylates
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Annulation reactions ofortho-substituted anilines and arylglyoxylates in the presence of K2S2O8at 80 °C under metal-free neutral conditions have been investigated, which extended a platform for the tandem synthesis of nitrogen heterocycles. While arylglyoxylic acids are known to undergo decarboxylation to form an acyl radical in the presence of K2S2O8and used in the Minisci acylation of electron-deficient (hetero)aromatics, their reactions with electron-richortho-substituted anilines to form nitrogen heterocycles have recently been studied. Depending upon the experimental conditions used in the reactions, the mechanism of the formation of heterocycles involving reactions of an acyl radical or aryl iminocarboxylic acids has been postulated. Given the subtle understanding of the mechanisms of annulation reactions of 2-substituted anilines and arylglyoxylates in the presence of K2S2O8, an extensive mechanistic investigation was undertaken. In the current study, the various mechanistic pathways including the generation of acyl, imidoyl, aminal, and N,O-hemiketal radicals have been postulated based on different possible decarboxylation modes. Some of the proposed intermediates are supported based on the available analytical data. The protocol uses a single, inexpensive reagent K2S2O8, which offers not only transition-metal-free conditions but also serves as the reagent for the key decarboxylation step. Taken together, this study complements the current development of the annulation reactions of 2-substituted anilines and arylglyoxylates in terms of synthesis and mechanistic understanding.
- Laha, Joydev K.,Panday, Surabhi,Tomar, Monika,Patel, Ketul V.
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supporting information
p. 845 - 853
(2021/02/09)
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- Visible-Light-Promoted Switchable Synthesis of C-3-Functionalized Quinoxalin-2(1H)-ones
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A visible-light-promoted synthesis of quinoxalin-2(1H)-ones has been developed using 9-mesityl-10-methylacridinium perchlorate as an organo-photocatalyst. The atmosphere-controlled method (Ar/air) enabled the selective synthesis of hydroxyl- and acyl-containing quinoxalin-2(1H)-ones under mild reaction conditions without the use of any metal catalysts or toxic reagents. A fluorescent labelling experiment showed that hydroxyl-containing quinoxalin-2(1H)-ones may have utility in various biological applications as potent fluorophores. (Figure presented.).
- Aganda, Kim Christopher C.,Hong, Boseok,Lee, Anna
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supporting information
p. 1443 - 1448
(2021/01/26)
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- K2S2O8mediated synthesis of 5-Aryldipyrromethanes and meso-substituted A4-Tetraarylporphyrins
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The synthesis of dipyrromethanes from pyrrole and arylglyoxylic acids in the presence of K2S2O8at 90 C is reported affording dipyrromethanes in very good yields. Unlike an excess pyrrole traditionally used in dipyrromethane synthesis, the current method uses a stoichiometric amount of pyrrole avoiding any use of Br?nsted or Lewis acid. A gram scale synthesis of 5-phenyldipyrromethane is also achieved demonstrating potential scale up of dipyrromethanes using this method feasible. Subsequently, dipyrromethanes were converted to A4tetraarylporphyrins also in the presence of K2S2O8at 90C. A direct synthesis of A4-tetraphenylporphyrin from excess pyrrole and phenylglyoxylic acid in the presence of K2S2O8 at 90C is also reported.
- Laha, Joydev K.,Hunjan, Mandeep Kaur
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p. 664 - 673
(2021/06/03)
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- Hypervalent Iodine(III)-Promoted Radical Oxidative C-H Annulation of Arylamines with α-Keto Acids
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A novel catalyst-free radical oxidative C-H annulation reaction of arylamines with α-keto acids toward benzoxazin-2-ones synthesis under mild conditions was developed. This hypervalent iodine(III)-promoted process eliminated the use of a metal catalyst or additive with high levels of functional group tolerance. Hypervalent iodine(III) was both an oxidant and a radical initiator for this reaction. The synthetic utility of this method was confirmed by the synthesis of the natural product cephalandole A.
- Long, Lipeng,Wang, Jieyan,Gu, Liuqing,Yang, Shiguang,Qiao, Liang,Luo, Guotian,Chen, Zhengwang
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supporting information
p. 12084 - 12092
(2021/08/24)
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- K2S2O8activation by glucose at room temperature for the synthesis and functionalization of heterocycles in water
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While persulfate activation at room temperature using glucose has primarily been focused on kinetic studies of the sulfate radical anion, the utilization of this protocol in organic synthesis is rarely demonstrated. We reinvestigated selected K2S2O8-mediated known organic reactions that invariably require higher temperatures and an organic solvent. A diverse, mild functionalization and synthesis of heterocycles using the inexpensive oxidant K2S2O8 in water at room temperature is reported, demonstrating the sustainability and broad scope of the method. Unlike traditional methods used for persulfate activation, the current method uses naturally abundant glucose as a K2S2O8 activator, avoiding the use of higher temperature, UV light, transition metals or bases.
- Hunjan, Mandeep Kaur,Laha, Joydev K.
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supporting information
p. 8437 - 8440
(2021/09/02)
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- Minisci aroylation of N-heterocycles using choline persulfate in water under mild conditions
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Metal persulfate mediated thermal oxidative organic transformations invariably require a higher temperature and frequently use an organic solvent. The objective of this work was to develop persulfate mediated oxidative transformations that can be performed nearly at room temperature using water as a solvent. This report describes modified Minisci aroylation of isoquinolines with arylglyoxylic acids using choline persulfate and its pre-composition (choline acetate and K2S2O8) in water at 40 °C. A few other nitrogen heterocycles were also utilized affording various aroylated products in good to excellent yields. Unlike metal persulfate that could produce metal salt byproducts, a key feature of the chemistry reported herein includes the use of environmentally benign choline persulfate containing biodegradable choline as a counter-cation, the Minisci reaction demonstrated at 40 °C in water as the only solvent, and unconventional activation of persulfate. This journal is
- Hunjan, Mandeep Kaur,Laha, Joydev K.,Tinwala, Ummehani
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p. 22853 - 22859
(2021/12/24)
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- Aroylation of Electron-Rich Pyrroles under Minisci Reaction Conditions
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The development of Minisci acylation on electron-rich pyrroles under silver-free neutral conditions has been reported featuring the regioselective monoacylation of (NH)-free pyrroles. Unlike conventional Minisci conditions, the avoidance of any acid that could result in the polymerization of pyrroles was the key to success. The umpolung reactivity of the nucleophilic acyl radical, generated in situ from arylglyoxylic acid, could help explain the mechanism of product formation with electron-rich pyrroles. Alternatively, the nucleophilic substitution of the acyl radical on the electron-deficient pyrrole radical cation is proposed.
- Laha, Joydev K.,Kaur Hunjan, Mandeep,Hegde, Shalakha,Gupta, Anjali
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supporting information
p. 1442 - 1447
(2020/02/22)
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- Selective photoredox decarboxylation of α-ketoacids to allylic ketones and 1,4-dicarbonyl compounds dependent on cobaloxime catalysis
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A photoredox/cobaloxime co-catalyzed coupling reaction of α-ketoacids and methacrylates to obtain allylic ketones is described. Without the cobaloxime catalyst, 1,4-dicarbonyl compounds are generated. The cobaloxime catalyst enables dehydrogenation to generate the formation of new olefins. The generality, good substrate scope and mild conditions are good features in the photoredox/cobaloxime catalysis protocol, and this method will provide new opportunities for the functionalization of more olefins.
- Zhang, Hong,Xiao, Qian,Qi, Xu-Kuan,Gao, Xue-Wang,Tong, Qing-Xiao,Zhong, Jian-Ji
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supporting information
p. 12530 - 12533
(2020/11/02)
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- Visible-Light-Induced Decarboxylative Cyclization/Hydrogenation Cascade Reaction to Access Phenanthridin-6-yl(aryl)methanol by an Electron Donor-Acceptor Complex
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A novel and efficient visible-light-induced decarboxylative cyclization/hydrogenation cascade reaction of α-oxocarboxylic acids and 2-isocyanobiaryls has been developed. Without the need of any external photosensitizer, oxidant, and reductant, this method offers a mild and green approach for the synthesis of diverse alcohols in moderate to good yields. A mechanism indicated that an electron donor-acceptor complex-driven decarboxylation, radical addition/cyclization, and in situ photochemical reduction of ketones to alcohols could be involved in the reaction.
- Shi, Wei,Ma, Fang,Li, Pinhua,Wang, Lei,Miao, Tao
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p. 13808 - 13817
(2020/11/20)
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- Metal-free benzoylation of imidazoheterocycles by oxidative decarboxylation of arylglyoxylic acids
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A simple and straightforward approach has been realized for the direct benzoylation of imidazoheterocycles by oxidative decarboxylation of arylglyoxylic acids in the presence of K2S2O8 as an oxidant. Various functional groups were tolerated on both imidazoheterocycles and arylglyoxylic acids and a wide range of C5-benzoyl-imidazoheterocycles were obtained in good to high yields (50-84%). Radical trapping experiments confirmed the involvement of the radical pathway. The developed protocol is amenable for a scale-up reaction. This journal is
- Jaspal, Sonam,Shinde, Vikki N.,Meena, Neha,Nipate, Dhananjay S.,Rangan, Krishnan,Kumar, Anil
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p. 9072 - 9080
(2020/11/27)
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- Synthesis of 2-thiopheneglyoxylic acid
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The invention belongs to the field of organic synthesis, in particular to synthesis of 2-thiopheneglyoxylic acid. Nitrosylsulfuric acid is used as oxidizing agent, reacts with 2-acetylthiophene in sulfuric acid solution, and then is refined to obtain 2-thiopheneglyoxylic acid. Refining is to pour the reaction solution into ice water, crystallize and filter, dissolve the obtained solid with alkali,adjust the pH to 2-5, add solvent to extract and remove impurities, and finally continue to add acid to adjust the pH to 0.8-1. The invention is a new method for preparing 2-thiopheneglyoxylic acid by using 2-acetylthiophene, in which no salt is generated, the solvent is not volatile, the equipment corrosion of volatile gases is reduced, the operating conditions are improved, and the purity of 2-thiopheneglyoxylic acid is above 98.5%, and the yield is above 81%. The mother liquor of the invention can be applied through simple treatment, thus reducing environmental pollution and being more environmentally friendly.
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Paragraph 0021--0028
(2020/01/03)
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- Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation
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The intermolecular radical addition to the carbonyl group is difficult due to the facile fragmentation of the resulting alkoxyl radical. To date, the intermolecular radical addition to ketones, a valuable approach to construct quaternary carbon centers, remains a formidable synthetic challenge. Here, we report the first visible-light-induced intermolecular alkyl boronic acid addition to α-ketoacids enabled by the Lewis acid activation. The in situ boron complex formation is confirmed by various spectroscopic measurements and mechanistic probing experiments, which facilitates various alkyl boronic acid addition to the carbonyl group and prevents the cleavage of the newly formed C-C bond. Diversely substituted lactates can be synthesized from readily available alkyl boronic acids and ketoacids at room temperature merely under visible light irradiation, without any additional reagent. This boron activation approach can be extended to alkyl dihydropyridines as radical precursors with external boron reagents for primary, secondary, and tertiary alkyl radical additions. The pharmaceutically useful anticholinergic precursors are easily scaled up in multigrams under metal-free conditions in flow reactors.
- Xie, Shasha,Li, Defang,Huang, Hanchu,Zhang, Fuyuan,Chen, Yiyun
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supporting information
p. 16237 - 16242
(2019/10/14)
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- Copper-catalyzed coupling of anthranils and α-keto acids: Direct synthesis of α-ketoamides
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Copper-catalyzed coupling of α-keto acids with anthranils is reported for the synthesis of α-ketoamides. This process involves N-O/C-O bond cleavages and C-N bond formation. Furthermore, the decarboxylation of α-keto acids can be successfully suppressed under redox-neutral conditions.
- Li, Ping-Gui,Zhu, Hao,Fan, Min,Yan, Cheng,Shi, Kai,Chi, Xi-Wen,Zou, Liang-Hua
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supporting information
p. 5902 - 5907
(2019/06/24)
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- Pd(OAc)2-Catalyzed Asymmetric Hydrogenation of α-Iminoesters
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An efficient Pd(OAc)2-catalyzed asymmetric hydrogenation of α-iminoesters was realized for the first time at 1 atm hydrogen pressure and room temperature. Pd(OAc)2, a less expensive Pd salt with low toxicity, was found to be the most suitable catalyst precursor rather than Pd(TFA)2 which is usually the catalyst of choice for homogeneous asymmetric hydrogenation. The chiral α-arylglycine fragments are widely found in many chiral products and bioactive molecules.
- Chen, Jianzhong,Li, Feilong,Wang, Fang,Hu, Yawen,Zhang, Zhenfeng,Zhao, Min,Zhang, Wanbin
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supporting information
p. 9060 - 9065
(2019/11/19)
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- Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand
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Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low temperature and exhibits excellent chemoselectivity toward primary amines.
- Tanaka, Kouichi,Miki, Takashi,Murata, Kunihiko,Yamaguchi, Ayumi,Kayaki, Yoshihito,Kuwata, Shigeki,Ikariya, Takao,Watanabe, Masahito
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p. 10962 - 10977
(2019/09/03)
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- Visible-Light-Triggered, Metal- and Photocatalyst-Free Acylation of N-Heterocycles
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A photoinduced acylation of N-heterocycles is explored. This visible-light triggered reaction occurs not only under extremely mild reaction conditions, but also does not require the presence of a photosensitizer. The mechanistic studies suggest formation of EDA complexes prompt to harness the energy from visible-light. Compatibility with a large panel of α-keto acids as acyl precursors and an array of N-heterocycles clearly showcase the synthetic potential of this handy and green acylation protocol. (Figure presented.).
- Guillemard, Lucas,Colobert, Fran?oise,Wencel-Delord, Joanna
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supporting information
p. 4184 - 4190
(2018/09/25)
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- Direct Acyl Radical Addition to 2 H-Indazoles Using Ag-Catalyzed Decarboxylative Cross-Coupling of α-Keto Acids
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A direct acyl radical addition to 2H-indazoles has been achieved for the first time, where the less-aromatic quinonoid 2H-indazoles readily accepted radical species to the C-3 position. Motivated by the lack of direct acylation strategy for 2H-indazoles, the current method utilizes the radical acceptability of 2H-indazoles, discovering an ambient temperature reaction to provide facile access to a diverse array of 3-acyl-2H-indazoles with three points of structural diversification in 25%-83% yields.
- Bogonda, Ganganna,Kim, Hun Young,Oh, Kyungsoo
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supporting information
p. 2711 - 2715
(2018/05/22)
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- Anti-Selective Catalytic Asymmetric Nitroaldol Reaction of α-Keto Esters: Intriguing Solvent Effect, Flow Reaction, and Synthesis of Active Pharmaceutical Ingredients
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A rare-earth metal/alkali metal bimetallic catalyst proved particularly effective for enantioselectively coupling nitroalkanes and α-keto esters in an anti-selective manner to afford synthetically versatile, densely functionalized, and optically active α-nitro tertiary alcohols. A chiral diamide ligand captured two distinct metal cations, giving rise to a catalytically competent solid-phase heterobimetallic catalyst by simple mixing via self-assembly. The advantage of the solid-phase asymmetric catalyst was realized by successful application to the enantio- and diastereoselective reaction in a continuous-flow platform. The use of closely related solvents in terms of structures and polarity parameters, THF and its methylated congener 2-Me-THF, had an unexpectedly large solvent effect both on the reaction rate and the stereoselectivity. The nitroaldol products share a privileged unit for active pharmaceutical ingredients, as demonstrated by the streamlined enantioselective synthesis of the marketed antifungal agents efinaconazole and albaconazole.
- Karasawa, Tomoya,Oriez, Rapha?l,Kumagai, Naoya,Shibasaki, Masakatsu
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supporting information
p. 12290 - 12295
(2018/09/27)
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- BENZO RING DERIVATIVE WITH B2 RECEPTOR AGONIST AND M3 RECEPTOR ANTAGONIST ACTIVITIES AND USE THEREOF IN MEDICINE
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A compound represented by general formula (I), or a stereoisomer, a hydrate, a metabolite, a solvate, a pharmaceutically acceptable salt, a cocrystal, or a prodrug thereof, the preparation method thereof, and use thereof in the manufacture of a medicament for treatment of an airway obstructive disease, wherein the substituents are defined as in the specification.
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Paragraph 0080-0082
(2018/09/29)
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- Industrial preparation method of heterocyclic derivative
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The invention provides an industrial preparation method of a heterocyclic derivative. The industrial preparation method of the heterocyclic derivative is characterized in that a heteroaryl derivative reacts with cyanate to generate a target compound. The preparation method is simple and different from a complex producing method with strict producing conditions in an existing technique, and the preparation method provided by the invention can achieve compounding of the target product through a step. According to the industrial preparation method of the heterocyclic derivative, a producing technique and a compounding route are optimized, so that in the producing process, side reactions are few, later treatment is convenient, producing conditions are mild, and the preparation method is suitable for industrial production models.
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Paragraph 0060-0062
(2017/08/24)
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- A Copper(I)-Catalyzed Addition/Annulation Sequence for the Two-Component Synthesis of γ-Ylidenebutenolides
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A highly efficient Cu(I)-catalyzed addition/annulation sequence has been developed for the synthesis of (Z)-ylidenebutenolides employing readily available α-ketoacids and alkynes as substrates. The reactions employ a simple commercially available Cu(I)-catalyst, display good substrate scope, and deliver products with high stereoselectivity. The synthetic utility of the method is demonstrated by the straightforward derivatization of the ylidenebutenolides into a diverse range of heterocycles, and also by the preparation of the natural product bovolide, and analogs thereof.
- Seo, Sangwon,Willis, Michael C.
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supporting information
p. 4556 - 4559
(2017/09/11)
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- Copper-catalyzed oxidative decarboxylative coupling of α-keto acids and sulfoximines
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A copper-catalyzed oxidative decarboxylative coupling of α-keto acids with NH-sulfoximines has been developed. With CuBr as the catalyst and K2S2O8 as the oxidant, this reaction enables the formation of a C-N bond and gives N-aroylsulfoximine products in moderate to excellent yields. The reaction mechanism is likely to involve the generation of a reactive aroyl radical intermediate.
- Pimpasri, Chaleena,Sumunnee, Ladawan,Yotphan, Sirilata
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supporting information
p. 4320 - 4327
(2017/07/10)
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- Aldehydes as Carbon Radical Acceptors: Silver Nitrate Catalyzed Cascade Decarboxylation and Oxidative Cyclization toward Dihydroflavonoid Derivatives
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Silver nitrate-catalyzed cascade decarboxylation and oxidative cyclization of α-oxocarboxylic acids, alkenes, and aldehydes is demonstrated for the first time. With ammonium persulfate as the oxidant, the cascade reactions afford dihydroflavonoid derivatives as products in moderate to good yields, exhibiting a broad substrate tolerance. Control experiments indicated that the mechanism includes a radical pathway with aldehydes as the carbon radical acceptors. (Figure presented.).
- Yang, Wen-Chao,Dai, Peng,Luo, Kai,Ji, Yi-Gang,Wu, Lei
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supporting information
p. 2390 - 2395
(2017/07/22)
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- Silver-catalyzed decarboxylative cross-coupling of α-keto acids with alkenes giving approach to chalcones
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A silver-catalyzed decarboxylative cross-coupling of α-keto acids with alkenes is reported. The method, with a wide range of substrate tolerance and mild operational conditions, can produce various chalcone derivatives in moderate to high yields from easily available starting materials.
- Wu, Shang,Yu, Hongheng,Hu, Qinzheng,Yang, Quanlu,Xu, Shouwang,Liu, Tian
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supporting information
p. 4763 - 4765
(2017/12/01)
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- AMINOESTER DERIVATIVES
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The invention relates to novel compounds which are both phosphodiesterase 4 (PDE4) enzymeinhibitorsand muscarinic M3 receptor antagonists, methods of preparing such compounds, compositions containing them and therapeutic use thereof.
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Page/Page column 80
(2016/12/22)
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- AMINOESTER DERIVATIVES
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The invention relates to novel compounds which are both phosphodiesterase 4 (PDE4) enzyme inhibitors and muscarinic M3 receptor antagonists, methods of preparing such compounds, compositions containing them and therapeutic use thereof.
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Page/Page column 60
(2016/11/21)
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- Palladium-catalyzed ortho-acylation of N-Nitrosoanilines with α-oxocarboxylic acids: A convenient method to synthesize N-Nitroso ketones and indazoles
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An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.
- Zhang, Liang,Wang, Zhe,Guo, Peiyu,Sun, Wei,Li, Ya-Min,Sun, Meng,Hua, Chengwen
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supporting information
p. 2511 - 2514
(2016/05/24)
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- Catalyst-Free Singlet Oxygen-Promoted Decarboxylative Amidation of α-Keto Acids with Free Amines
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A novel catalyst-free decarboxylative amidation of α-keto acids with amines under mild conditions has been developed. Advantages of the new protocol include avoidance of metal catalysts and high levels of functional group tolerance. In addition, the reaction can be scaled up and shows high chemoselectivity. Preliminary mechanistic studies suggest that singlet oxygen, generated from oxygen under irradiation, is the key promoter for this catalyst-free transformation.
- Xu, Wen-Tao,Huang, Bei,Dai, Jian-Jun,Xu, Jun,Xu, Hua-Jian
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supporting information
p. 3114 - 3117
(2016/07/14)
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- Silver-promoted decarboxylative amidation of α-keto acids with amines
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A general and effective method for the synthesis of amides through decarboxylative amidation of α-keto acids with amines has been developed. The reaction proceeded smoothly to afford the corresponding amide products in good yield under air and shows excellent functional group tolerance. In addition, the protocol can be further applied in the synthesis of heterocyclic compounds like benzimidazoles.
- Xu, Xiao-Lan,Xu, Wen-Tao,Wu, Ji-Wei,He, Jian-Bo,Xu, Hua-Jian
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supporting information
p. 9970 - 9973
(2016/11/06)
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- Copper-catalyzed direct α-ketoesterification of propiophenones with acetophenones via C(sp3)-H oxidative cross-coupling
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A novel copper-catalyzed direct α-ketoesterification of propiophenones with acetophenones via C(sp3)-H oxidative cross-coupling was developed. The reaction utilized O2 as a clean oxidant with high atom economy and the starting materials are facile and commercially available.
- Du, Juan,Zhang, Xiuli,Sun, Xi,Wang, Lei
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supporting information
p. 4372 - 4375
(2015/03/30)
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- Synthesis of oxazoles by silver catalysed oxidative decarboxylation-cyclization of α-oxocarboxylates and isocyanides
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A silver catalysed synthesis of oxazoles by the oxidative decarboxylation-cyclization of α-oxocarboxylates and isocyanides was developed. This method provided a novel strategy to construct oxazole rings compared to traditional methods. Mechanistic investigations such as operando IR, EPR and radical inhibition experiments were carefully done and confirmed the acyl cation and Ag(ii) as the intermediates in this transformation, and the involvement of a radical decarboxylative process.
- Ma, Yiyang,Yan, Zhiyuan,Bian, Changliang,Li, Ke,Zhang, Xiaowen,Wang, Mengfan,Gao, Xinlong,Zhang, Heng,Lei, Aiwen
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supporting information
p. 10524 - 10527
(2015/06/25)
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- Enantio- and chemoselective Br?nsted-acid/Mg(nBu) 2 catalysed reduction of α-keto esters with catecholborane
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The first enantio- and chemoselective Br?nsted-acid catalysed reduction of α-keto esters with catecholborane has been developed. The α-hydroxy esters were obtained under mild reaction conditions in virtually quantitative yields and excellent enantioselectivities. With slight modifications both enantiomers can be obtained without any loss of selectivity. This journal is the Partner Organisations 2014.
- Enders, Dieter,St?ckel, Bianca A.,Rembiak, Andreas
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supporting information
p. 4489 - 4491
(2014/04/17)
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- Visible-light-mediated decarboxylation/oxidative amidation of α-keto acids with amines under mild reaction conditions using O2
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Photochemistry has ushered in a new era in the development of chemistry, and photoredox catalysis has become a hot topic, especially over the last five years, with the combination of visible-light photoredox catalysis and radical reactions. A novel, simple, and efficient radical oxidative decarboxylative coupling with the assistant of the photocatalyst [Ru(phen)3]Cl 2 is described. Various functional groups are well-tolerated in this reaction and thus provides a new approach to developing advanced methods for aerobic oxidative decarboxylation. The preliminary mechanistic studies revealed that: 1)an SET process between [Ru(phen)3]2+* and aniline play an important role; 2)O2 activation might be the rate-determining step; and 3)the decarboxylation step is an irreversible and fast process. Bring to light: A new approach to oxidative decarboxylation under visible light using O2 as the oxidant has been developed. A variety of functional groups were well-tolerated in this reaction and insights into the mechanism were investigated with the assistance of EPR spectroscopy, cyclic voltammetry, and theoretical studies.
- Liu, Jie,Liu, Qiang,Yi, Hong,Qin, Chu,Bai, Ruopeng,Qi, Xiaotian,Lan, Yu,Lei, Aiwen
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supporting information
p. 502 - 506
(2014/01/23)
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- Synthesis of 6-acyl phenanthridines by oxidative radical decarboxylation-cyclization of α-oxocarboxylates and isocyanides
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A silver catalysed synthesis of 6-acyl phenanthridines by oxidative radical decarboxylation-cyclization of α-oxocarboxylates and isocyanides was developed. This reaction provided a novel method to realize C1 insertion via a radical process and various functional groups were well-tolerated. The Royal Society of Chemistry.
- Liu, Jie,Fan, Chao,Yin, Hongyu,Qin, Chu,Zhang, Guoting,Zhang, Xu,Yi, Hong,Lei, Aiwen
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supporting information
p. 2145 - 2147
(2014/02/14)
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- Palladium-catalyzed decarboxylative acylation of O-methyl ketoximes with α-keto acids
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A mild, practical and efficient palladium-catalyzed decarboxylative ortho-acylation of O-methyl ketoximes with α-keto acids via C-H bond activation is described. In these reactions, a broad range of O-methyl ketoximes and α-keto acids undergoes the decarboxylative cross-coupling reactions with high selectivities and good tolerance. The Royal Society of Chemistry 2013.
- Kim, Minyoung,Park, Jihye,Sharma, Satyasheel,Kim, Aejin,Park, Eonjeong,Kwak, Jong Hwan,Jung, Young Hoon,Kim, In Su
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supporting information
p. 925 - 927
(2013/02/23)
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- Pd-catalyzed decarboxylative ortho-acylation of O-methyl oximes with phenylglyoxylic acids
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Aryl ketones were synthesized via Pd-catalyzed decarboxylative coupling between O-methyl oximes and phenylglyoxylic acids using (NH4) 2S2O8 as the oxidant. The Royal Society of Chemistry 2013.
- Yang, Zhiyong,Chen, Xiang,Liu, Jidan,Gui, Qingwen,Xie, Kai,Li, Miaomiao,Tan, Ze
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supporting information
p. 1560 - 1562
(2013/03/13)
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- Palladium-catalyzed decarboxylative acylation of O-phenyl carbamates with α-oxocarboxylic acids at room temperature
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A palladium-catalyzed oxidative acylation of O-phenyl carbamates with α-oxocarboxylic acids via selective aromatic C-H bond activation is described. This protocol represents the first ortho-acylation of phenol derivatives, and a catalytic amount of triflic acid additive is crucial for this transformation. Copyright
- Sharma, Satyasheel,Kim, Aejin,Park, Eonjeong,Park, Jihye,Kim, Minyoung,Kwak, Jong Hwan,Lee, Sang Hwi,Jung, Young Hoon,Kim, In Su
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supporting information
p. 667 - 672
(2013/04/11)
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- Palladium-catalyzed decarboxylative coupling of α-oxocarboxylic acids with C(sp2)-H of 2-aryloxypyridines
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An efficient palladium-catalyzed decarboxylative ortho-acylation of 2-aryloxypyridines with α-oxocarboxylic acids is described. In this new transformation, the aromatic C(sp2)-H bond was successfully acylated to give diverse aromatic ketones regioselectively in moderate to good yields. The pyridine group can be removed easily after the acylation to give the corresponding 2-hydroxy aromatic ketones. Copyright
- Yao, Jinzhong,Feng, Ruokun,Wu, Zaihong,Liu, Zhanxiang,Zhang, Yuhong
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supporting information
p. 1517 - 1522
(2013/06/27)
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- Decarboxylative acylation of cyclic enamides with α-oxocarboxylic acids by palladium-catalyzed C-H activation at room temperature
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An efficient catalytic decarboxylative acylation of unactivated sp 2 (alkenyl) C-H bonds has been developed. Various substituted α-oxocarboxylic acids with different electronic properties react under mild conditions to afford a diverse range of β-acyl enamide products in good yields. The reaction is proposed to proceed via a cyclic vinylpalladium intermediate, facilitating the decarboxylative dehydrogenative process with enamide coupling partners.
- Wang, Hua,Guo, Li-Na,Duan, Xin-Hua
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supporting information
p. 4358 - 4361
(2012/10/29)
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- Asymmetrie aerobic oxidation of α-hydroxy acid derivatives by C 4-symmetric, vanadate-centered, tetrakisvanadyl(V) clusters derived from N-salicylidene-α-aminocarboxylates
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(Chemical Equation Presented) A series of chiral vanadyl(V) methoxides bearing 3-t-butyl-5-substituted N-salicylene-L-valinate and L-t-leucinate as chiral auxiliaries has been prepared. In all cases except the 3,5-di-t-butyl analogue, they exist as monomers both in solution and in the single crystal state. In the case of the 3,5-di-t-butyl analogue, the architectural nature of the vanadyl(V) complex highly depends on the base used during the complex formation event. A pentanuclear C4-symmetric complex was formed when potassium salts were employed instead of the corresponding sodium salts. A central vanadate(V) unit serves to grip four identical chiral monomelic vanadyl(V) units together, by which a potassium ion sits on top of the four flanking units through carbonyl coordinations and serves to hold the whole cluster by cooperation with the central vanadate(V) unit. In comparison with the corresponding monomelic vanadyl(V) methoxide complex, the cluster complex was utilized to facilitate the asymmetric aerobic oxidations of various racemic α-hydroxyesters, -amides, and -thioesters with excellent selectivity factors (krel 40 to >500).
- Chen, Chien-Tien,Bettigeri, Sampada,Weng, Shiue-Shien,Pawar, Vijay D.,Lin, Ya-Hui,Liu, Cheng-Yuan,Lee, Way-Zen
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p. 8175 - 8185
(2008/02/13)
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- COBALT-CATALYZED LOW PRESSURE DOUBLE CARBONYLATION OF ARYL AND SECONDARY BENZYL HALIDES
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α-Ketoacids can be easily synthesized with satisfactory yields and selectivities by carbonylation of aryl halides and secondary benzyl halides under very mild conditions.The reactions are catalyzed by Co2(CO)8 in alcoholic solvents; the presence of a methyl source (dimethyl sulfate or methyl iodide) is necessary for the carbonylation of the aryl halides.Base, temperature and solvent have large effects on the course of the reaction.
- Francalanci, F.,Bencini, E.,Gardano, A.,Vincenti, M.,Foa, M.
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p. C27 - C30
(2007/10/02)
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- Process for preparing thienylglyoxylic acids and amides
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Thienylglyoxylic acids and/or amides thereof are prepared by reacting thiophene carboxylic acid chloride with sodium cyanide and hydrolyzing the resulting product in a strong mineral acid.
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