- Reaction of naphthalene-2,3-dicarbaldehyde with cyanide; a unique oxidative condensation product
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Naphthalene-2,3-dicarbaldehyde (NDA), a reagent used for the fluorescent detection of amino acids in the presence of cyanide, self-condenses in the presence of cyanide ion and methanol at room temperature to yield a unique crystalline product 2, 15-hydroxybenzo[g]benzo[6,7]isochromeno[4,3-c]isochromen- 7(15H)-one. The product is proposed to result from facile air oxidation of NDA to a methyl ester in combination with benzoin condensation. Product 2 does not to form in the absence of air. The gHMBC spectrum of 2 distinguishes it from a possible alternative isomeric condensation product.
- McGill, Colin M.,Swearingen, Kristian E.,Drew, Kelly L.,Rasley, Brian T.,Green, Thomas K.
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Read Online
- HCl-Catalyzed Aerobic Oxidation of Alkylarenes to Carbonyls
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The construction of C?O bonds through C?H bond functionalization remains fundamentally challenging. Here, a practical chlorine radical-mediated aerobic oxidation of alkylarenes to carbonyls was developed. This protocol employed commercially available HCl as a hydrogen atom transfer (HAT) reagent and air as a sustainable oxidant. In addition, this process exhibited excellent functional group tolerance and a broad substrate scope without the requirement for external metal and oxidants. The mechanistic hypothesis was supported by radical trapping, 18O labeling, and control experiments.
- Niu, Kaikai,Shi, Xiaodi,Ding, Ling,Liu, Yuxiu,Song, Hongjian,Wang, Qingmin
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- Visible light-mediated, high-efficiency oxidation of benzyl to acetophenone catalyzed by fluorescein
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An environmentally friendly aerobic oxidation of benzyl C(sp3)-H bonds to ketones via selective oxidation catalysis was developed. Fluorescein is an efficient photocatalyst with excellent chemical selectivity. The reaction has a wide substrate scope, and a successful gram-scale experiment demonstrated its potential industrial utility.
- Geng, Haoxing,Liu, Xin,Zhu, Qing
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supporting information
(2021/12/20)
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- Carboxyl Methyltransferase Catalysed Formation of Mono- and Dimethyl Esters under Aqueous Conditions: Application in Cascade Biocatalysis
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Carboxyl methyltransferase (CMT) enzymes catalyse the biomethylation of carboxylic acids under aqueous conditions and have potential for use in synthetic enzyme cascades. Herein we report that the enzyme FtpM from Aspergillus fumigatus can methylate a broad range of aromatic mono- and dicarboxylic acids in good to excellent conversions. The enzyme shows high regioselectivity on its natural substrate fumaryl-l-tyrosine, trans, trans-muconic acid and a number of the dicarboxylic acids tested. Dicarboxylic acids are generally better substrates than monocarboxylic acids, although some substituents are able to compensate for the absence of a second acid group. For dicarboxylic acids, the second methylation shows strong pH dependency with an optimum at pH 5.5–6. Potential for application in industrial biotechnology was demonstrated in a cascade for the production of a bioplastics precursor (FDME) from bioderived 5-hydroxymethylfurfural (HMF).
- Ashbrook, Chloe,Carnell, Andrew J.,Goulding, Ellie,Hatton, Harry,Johnson, James R.,Kershaw, Neil M.,McCue, Hannah V.,Rigden, Daniel J.,Ward, Lucy C.
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supporting information
(2022/02/21)
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- Novel Bortezomib prodrug and the use thereof
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A compound of formula 1 of the invention. The optical isomer or a pharmaceutically acceptable salt thereof is a composition for bone targeting drug delivery by covalently linking a bone directional ligand binding to bone to bortezomib to overcome the tech
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Paragraph 0088; 0090-0092; 0094-0096
(2021/07/20)
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- Heterocyclic compound as well as preparation method and application thereof
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The invention discloses an immune checkpoint inhibitor heterocyclic compound capable of blocking a VISTA signal path as well as a preparation method and application thereof. The compound is shown as aformula I which is described in the specification. The
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Paragraph 0120-0125
(2021/02/06)
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- Metal- And additive-free C-H oxygenation of alkylarenes by visible-light photoredox catalysis
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A metal- and additive-free methodology for the highly selective, photocatalyzed C-H oxygenation of alkylarenes under air to the corresponding carbonyls is presented. The process is catalyzed by an imide-acridinium that forms an extremely strong photooxidant upon visible light irradiation, which is able to activate inert alkylarenes such as toluene. Hence, this is an easy to perform, sustainable and environmentally friendly oxidation that provides valuable carbonyls from abundant, readily available compounds.
- García Manche?o, Olga,Kuhlmann, Jan H.,Pérez-Aguilar, María Carmen,Piekarski, Dariusz G.,Uygur, Mustafa
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supporting information
p. 3392 - 3399
(2021/05/21)
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- METHOD FOR OXIDATIVE CLEAVAGE OF COMPOUNDS WITH UNSATURATED DOUBLE BOND
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A method for oxidative cleavage of a compound with an unsaturated double bond is provided. The method comprises the following step: (A) providing a compound (I) with an unsaturated double bond, a reagent with trifluoromethyl, and a catalyst; wherein the catalyst is represented by the following formula (II): M(O)mL1yL2z (II); wherein, M, L1, L2, m, y, z, R1, R2 and R3 are defined in the specification; and (B) mixing the compound with an unsaturated double bond and the reagent with a trifluoromethyl to perform an oxidation of the compound with the unsaturated double bond by using the catalyst at air or an oxygen condition to get a compound presented as formula (III):
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Paragraph 0053-0056
(2021/03/19)
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- PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
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A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
- Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
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p. 491 - 497
(2021/01/20)
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- Organotellurium-catalyzed oxidative deoximation reactions using visible-light as the precise driving energy
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Irradiated by visible light, the recyclable (PhTe)2-catalyzed oxidative deoximation reaction could occur under mild conditions. In comparison with the thermo reaction, the method employed reduced catalyst loading (1 mol% vs. 2.5 mol%), but afforded elevated product yields with expanded substrate scope. This work demonstrated that for the organotellurium-catalyzed reactions, visible light might be an even more precise driving energy than heating because it could break the Te–Te bond accurately to generate the active free radical catalytic intermediates without damaging the fragile substituents (e.g., heterocycles) of substrates. The use of O2 instead of explosive H2O2 as oxidant affords safer reaction conditions from the large-scale application viewpoint.
- Deng, Xin,Qian, Rongrong,Zhou, Hongwei,Yu, Lei
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supporting information
p. 1029 - 1032
(2020/10/23)
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- Luminescent Platinum(II) Complexes with Bidentate Diacetylide Ligands: Structures, Photophysical Properties and Application Studies
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A series of platinum(II) complexes supported by terphenyl diacetylide as well as diimine or bis-N-heterocyclic carbene (NHC) ligands have been prepared. The diacetylide ligands adopt a cis coordination mode featuring non-planar terphenyl moieties as revealed by X-ray crystallographic analyses. The electrochemical, photophysical and photochemical properties of these platinum(II) complexes have been investigated. These platinum(II) diimine complexes show broad emission with peak maxima from 566 nm to 706 nm, with two of them having emission quantum yields >60% and lifetimes 2 μs in solutions at room temperature, whereas the platinum(II) diacetylide complexes having bis-N-heterocyclic carbene instead of diimine ligand display photoluminescence with quantum yields of up to 28% in solutions and excited state lifetimes of up to 62 μs at room temperature. Application studies revealed that one of the complexes can catalyze photoinduced aerobic dehydrogenation of alcohols and alkenes, and a relatively non-toxic water-soluble Pt(II) complex displays anti-angiogenic activity.
- Luo, Zaoli,Liu, Yungen,Tong, Ka-Chung,Chang, Xiao-Yong,To, Wai-Pong,Che, Chi-Ming
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p. 2978 - 2992
(2021/08/30)
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- INHIBITOR COMPOUNDS FOR MALE CONTRACEPTION
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Pyrazole compounds and piperazine compounds that are inhibitors of ALDH1A1 and ALDH1A2 and methods for using the pyrazole compounds and piperazine compounds in male contraceptive compositions for preventing spermatogenesis.
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Page/Page column 36
(2020/07/07)
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- Rapid Organocatalytic Formation of Carbon Monoxide: Application towards Carbonylative Cross Couplings
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Herein, the first organocatalytic method for the transformation of non-derivatized formic acid into carbon monoxide (CO) is introduced. Formylpyrrolidine (FPyr) and trichlorotriazine (TCT), which is a cost-efficient commodity chemical, enable this decarbonylation. Utilization of dimethylformamide (DMF) as solvent and catalyst even allows for a rapid CO generation at room temperature. Application towards four different carbonylative cross coupling protocols demonstrates the high synthetic utility and versatility of the new approach. Remarkably, this also comprehends a carbonylative Sonogashira reaction at room temperature employing intrinsically difficult electron-deficient aryl iodides. Commercial 13C-enriched formic acid facilitates the production of radiolabeled compounds as exemplified by the pharmaceutical Moclobemide. Finally, comparative experiments verified that the present method is highly superior to other protocols for the activation of carboxylic acids.
- Zoller, Ben,Zapp, Josef,Huy, Peter H.
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supporting information
p. 9632 - 9638
(2020/07/13)
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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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- Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
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An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
- Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
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supporting information
p. 17887 - 17896
(2020/08/19)
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- Method for synthesizing tertiary alcohol by catalytically oxidizing benzyl tertiary C-H bonds of aromatic hydrocarbon through metalloporphyrin
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The invention discloses a method for synthesizing tertiary alcohol by catalytically oxidizing benzyl tertiary C-H bonds of aromatic hydrocarbon through metalloporphyrin. The method comprises the following steps: dispersing metalloporphyrin (1*10-1%, mol/mol) into aromatic hydrocarbon; sealing the reaction system, heating to 40-120 DEG C while stirring, introducing an oxidant (0.10-1.0 MPa), keeping the set temperature and pressure, carrying out reactions for 3.0-24.0 hours under stirring, and carrying out after-treatment on the reaction solution to obtain the product aromatic benzyl tertiary alcohol. The method has the advantages of shortest conversion path, highest atom economy, lower reaction temperature, lower environmental influence and the like, and the selectivity of aromatic benzyl tertiary alcohol is high. In addition, the content of aromatic hydrocarbon hydroperoxide is low, and the safety coefficient is high. The invention provides an efficient, feasible and safe method for synthesizing aromatic benzyl tertiary alcohol through selective catalytic oxidation of benzyl tertiary C-H bonds of aromatic hydrocarbon.
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Paragraph 0070-0071
(2020/09/30)
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- Fluoro-Substituted Methyllithium Chemistry: External Quenching Method Using Flow Microreactors
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The external quenching method based on flow microreactors allows the generation and use of short-lived fluoro-substituted methyllithium reagents, such as fluoromethyllithium, fluoroiodomethyllithium, and fluoroiodostannylmethyllithium. Highly chemoselective reactions have been developed, opening new opportunities in the synthesis of fluorinated molecules using fluorinated organometallics.
- Colella, Marco,Degennaro, Leonardo,Higuma, Ryosuke,Ishikawa, Susumu,Luisi, Renzo,Nagaki, Aiichiro,Takahashi, Yusuke,Tota, Arianna
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p. 10924 - 10928
(2020/05/08)
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- Pd/C-Catalyzed methoxycarbonylation of aryl chlorides
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A new protocol for the methoxycarbonylation of aryl chlorides has been developed. Various methyl benzoates were produced in good to excellent yields. Several parameters are crucial for the success of this procedure: 1) the usage of LiOMe as the base or co-nucleophile which facilitate the carbonylative transformation; 2) employing Pd/C as the catalyst to prevent the palladium reduced by MeOH and subsequent agglomerate; 3) CO concentration, excessive CO concentration will directly lead to the termination of the reaction.
- Ai, Han-Jun,Franke, Robert,Wu, Xiao-Feng
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- Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
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Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
- Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
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supporting information
p. 7683 - 7689
(2020/04/22)
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- Manganese/Copper Co-catalyzed Electrochemical Wacker-Tsuji-Type Oxidation of Aryl-Substituted Alkenes
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A manganese/copper co-catalyzed electrochemical Wacker-Tsuji-type oxidation of aryl-substituted alkenes has been developed. The process involves the use of 5 mol % MnBr2 and 7.5 mol % CuCl2, in 4:1 acetonitrile/water in an undivided cell at 60 °C, with 2.8 V constant applied potential. α-Aryl ketones are formed in moderate to excellent yields, with the advantages of avoidance of palladium as a catalyst and any external chemical oxidant in an easily operated, cost-effective procedure.
- Lai, Junshan,Pericàs, Miquel A.
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supporting information
p. 7338 - 7342
(2020/10/02)
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- Hydration of terminal alkynes catalyzed by cobalt corrole complex
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Cobalt(III) corrole was firstly applied to the hydration of terminal alkynes. The alkyne hydration proceeded in good to excellent yield with 0.03 to 0.3 mol% cobalt corrole catalyst loading. A wide range of substrates were tolerated. Particularly, the reaction can give 90% yield in a gram scale experiment.
- Lai, Jia-Wei,Liu, Zhao-Yang,Chen, Xiao-Yan,Zhang, Hao,Liu, Hai-Yang
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supporting information
(2020/10/02)
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- A Deoximation Method for Deprotection of Ketones and Aldhydes Using a Graphene-Oxide-Based Co-catalysts System
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The deoximation of a wide range of ketoximes and aldoximes to their corresponding carbonyl compounds with high yields has been achieved using graphene oxide (GO) and sodium nitrite (NaNO2) as highly efficient catalysts and air as the green oxidant under mild conditions. The mechanism of deprotection and recycling use of catalyst were revealed in deep experiment. The carboxylic acid groups on the GO were essential for high catalytic activity. (Figure presented.).
- Tong, Qiaolin,Liu, Yang,Gao, Xuezhi,Fan, Zhanfang,Liu, Tianfu,Li, Bo,Su, Dangsheng,Wang, Qinghe,Cheng, Maosheng
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supporting information
p. 3137 - 3145
(2019/05/01)
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- Method for removing acyl group in diazo of aryl diazonium salt
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The invention provides a method for removing an acyl group in diazo of an aryl diazonium salt. The method is characterized in that the aryl diazonium salt and its derivative and an ortho-dicarbonyl compound undergo an illumination reaction to obtain a corresponding arylacyl product. The method has the advantages of high yield of the product, no metal involvement, and simple process.
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Paragraph 0052; 0071-0073; 0088
(2019/02/13)
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- Transfer-dehydrogenation of secondary alcohols catalyzed by manganese NNN-pincer complexes
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Novel catalytic systems based on pentacarbonylmanganese bromide and stable NNN-pincer ligands are presented for the transfer-dehydrogenation of secondary alcohols to give the corresponding ketones in good to excellent isolated yields. Best results are obtained using di-picolylamine derivatives as ligands and acetone as an inexpensive hydrogen acceptor. Besides high activity for benzylic substrates, aliphatic alcohols, as well as steroid derivatives, are readily oxidized in the presence of the optimal phosphorus-free catalyst.
- Budweg, Svenja,Junge, Kathrin,Beller, Matthias
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supporting information
p. 14143 - 14146
(2019/12/02)
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- PYRIMIDINONE DERIVATIVES AND USES THEREOF TO NEUTRALIZE THE BIOLOGICAL ACTIVITY OF CHEMOKINES
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A subject of the present invention is a compound having the general formula (I) a pharmaceutically acceptable salt thereof or a tautomeric form thereof, wherein A, B3, B4, B5, Y, X, B1 and B2 are as defined in any one of claims 1 to 10. Another subject of the invention is the compound as defined above for use as a medicament, in particular for preventing and/or treating inflammation and inflammatory diseases, immune and auto-immune diseases, pain related diseases, genetic diseases and/or cancer.
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Page/Page column 44
(2018/02/28)
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- Thiyl radical promoted chemo- and regioselective oxidation of CC bonds using molecular oxygen: Via iron catalysis
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The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage of alkenes using molecular oxygen (1 atm) has been developed. The reaction proceeds under mild reaction conditions with high efficiency and high chemo- and regioselectivity. It features a broad substrate scope and excellent functional group compatibility, enabling facile access to valuable molecules for application in medicinal chemistry. Preliminary mechanistic studies reveal that a vital intermediate dioxetane might be involved in the reaction and a thiyl radical plays a synergistic role in facilitating the selective oxidation of the CC bond.
- Xiong, Baojian,Zeng, Xiaoqin,Geng, Shasha,Chen, Shuo,He, Yun,Feng, Zhang
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supporting information
p. 4521 - 4527
(2018/10/17)
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- Biomimetic Oxidative Deamination Catalysis via ortho-Naphthoquinone-Catalyzed Aerobic Oxidation Strategy
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An ortho-naphthoquinone-catalyzed oxidative deamination reaction has been developed where the molecular oxygen and water serve as the sole oxidant and nucleophile. The current aerobic deamination reaction proceeds via the ketimine formation between ortho-naphthoquinones and amines followed by the prototropic rearrangement and hydrolysis by water, representing a biomimetic oxidative deamination of amine species in the human body by the liver and kidneys. The compatibility of ortho-naphthoquinone organocatalysts with molecular oxygen and water opens up a new biomimetic catalyst system that can function as versatile deaminases for a variety of amine-containing molecules such as amino acids and DNA nuclear bases.
- Golime, Gangadhararao,Bogonda, Ganganna,Kim, Hun Young,Oh, Kyungsoo
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p. 4986 - 4990
(2018/05/14)
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- Conversion of Olefins into Ketones by an Iron-Catalyzed Wacker-type Oxidation Using Oxygen as the Sole Oxidant
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We describe a mild and operationally simple procedure for the oxidation of olefins into ketones. The reaction is catalyzed by the hexadecafluorinated iron–phthalocyanine complex FePcF16 with stoichiometric amounts of triethylsilane as an additive under oxygen atmosphere to give ketones in good to high yields with excellent chemoselectivity and functional group tolerance. Ketone formation proceeds in up to 95 % yield and with 100 % regioselectivity while the corresponding alcohols were observed as side products.
- Puls, Florian,Kn?lker, Hans-Joachim
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supporting information
p. 1222 - 1226
(2018/01/01)
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- PtO2/PTSA system catalyzed regioselective hydration of internal arylalkynes bearing electron withdrawing groups
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A highly efficient PtO2/PTSA catalyst system for the hydration of a wide array of alkynes was developed. This method proved to be compatible with a large range of functional groups and the ketone products were obtained in high yields. The scope of this methodology was also extended to the synthesis of 3-Aryl-isochromenones,-indoles and-benzofurans.
- Lin, Hsin-Ping,Ibrahim, Nada,Provot, Olivier,Alami, Mouad,Hamze, Abdallah
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p. 11536 - 11542
(2018/04/05)
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- Transition-Metal- and Halogen-Free Oxidation of Benzylic sp 3 C-H Bonds to Carbonyl Groups Using Potassium Persulfate
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Aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids are prepared from benzyl substrates using potassium persulfate as oxidant with catalytic pyridine in acetonitrile under mild conditions. Neither transition metals nor halogens are involved in the reactions.
- Hu, Yixin,Zhou, Lihong,Lu, Wenjun
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p. 4007 - 4016
(2017/08/29)
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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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- Organopromoted Selectivity-Switchable Synthesis of Polyketones
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In this work, an organopromoted metal-free pharmaceutical-oriented selectivity-switchable benzylic oxidation was developed, affording mono-, di-, and trioxygenation products, respectively, using oxygen as the oxidant under mild conditions. This process facilitates dioxygenation of 2,6-benzylic positions of heterocycles, which could be inhibited by heterocycle chelation to the metal cocatalysts. Enantiopure chiral ketones could also be prepared. The noninvolvement of transition metals and toxins avoids metal or hazardous residues, consequently ensuring a final-stage gram-scale synthesis of Lenperone.
- Liu, Jie,Hu, Kang-Fei,Qu, Jian-Ping,Kang, Yan-Biao
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supporting information
p. 5593 - 5596
(2017/10/25)
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- A phosphine-free, heterogeneous palladium-catalyzed atom-efficient carbonylative cross-coupling of triorganoindiums with aryl halides leading to unsymmetrical ketones
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The first phosphine-free heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl halides with triorganoindiums has been developed that proceeds smoothly under 1 or 2.5 atm of carbon monoxide in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable unsymmetrical ketones with high atom-economy, good yield, and recyclability of the catalyst. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
- You, Shengyong,Xiao, Ruian,Liu, Haiyi,Cai, Mingzhong
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p. 13862 - 13870
(2017/11/27)
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- Visible-Light-Driven Carboxylation of Aryl Halides by the Combined Use of Palladium and Photoredox Catalysts
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A highly useful, visible-light-driven carboxylation of aryl bromides and chlorides with CO2 was realized using a combination of Pd(OAc)2 as a carboxylation catalyst and Ir(ppy)2(dtbpy)(PF6) as a photoredox catalyst. This carboxylation reaction proceeded in high yields under 1 atm of CO2 with a variety of functionalized aryl bromides and chlorides without the necessity of using stoichiometric metallic reductants.
- Shimomaki, Katsuya,Murata, Kei,Martin, Ruben,Iwasawa, Nobuharu
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p. 9467 - 9470
(2017/07/24)
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- Dehydrogenative oxidation of alcohols in aqueous media catalyzed by a water-soluble dicationic iridium complex bearing a functional N-heterocyclic carbene ligand without using base
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A dicationic iridium complex bearing a bidentate ligand that comprises N-heterocyclic carbene and α-hydroxypyridine moieties has been designed and synthesized. The complex exhibited high catalytic performance in aqueous media for the dehydrogenative oxidation of secondary alcohols to ketones accompanying the evolution of hydrogen. Furthermore, dehydrogenative transformation of primary alcohols to the carboxylic acids in aqueous media was also catalyzed by the complex without using base.
- Fujita, Ken-Ichi,Tamura, Ryuichi,Tanaka, Yuhi,Yoshida, Masato,Onoda, Mitsuki,Yamaguchi, Ryohei
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p. 7226 - 7230
(2017/11/09)
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- Acceptorless Dehydrogenation of Alcohols Catalyzed by CuI N-Heterocycle Thiolate Complexes
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CuI N-heterocycle thiolate clusters efficiently catalyze the acceptorless dehydrogenation of alcohols at 70 °C. A variety of secondary/primary benzylic, allylic, and aliphatic alcohols are dehydrogenated to the corresponding ketones and aldehydes in high yields of isolated product upon release of H2. This simple catalytic system is involved in the synthesis of imines through the one-pot reaction of alcohols and amines.
- Tan, Da-Wei,Li, Hong-Xi,Zhang, Meng-Juan,Yao, Jian-Lin,Lang, Jian-Ping
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p. 1113 - 1118
(2017/03/27)
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- Chemoselective Continuous Ru-Catalyzed Hydrogen-Transfer Oppenauer-Type Oxidation of Secondary Alcohols
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A continuous flow method for the selective oxidation of secondary alcohols is reported. The method is based on an Oppenauer-type ruthenium-catalyzed hydrogen-transfer process that uses acetone as both solvent and oxidant. The process utilizes a low loading (1 mol%) of the commercially available ruthenium catalyst [Ru(p-cymene)Cl2]2 and triethylamine as a base and can be successfully applied to a range of different substrates, with a good level of functional group tolerance.
- Labes, Ricardo,Battilocchio, Claudio,Mateos, Carlos,Cumming, Graham R.,De Frutos, Oscar,Rincón, Juan A.,Binder, Kellie,Ley, Steven V.
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supporting information
p. 1419 - 1422
(2017/09/23)
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- Synthesis of Ketones and Esters from Heteroatom-Functionalized Alkenes by Cobalt-Mediated Hydrogen Atom Transfer
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Cobalt bis(acetylacetonate) is shown to mediate hydrogen atom transfer to a broad range of functionalized alkenes; in situ oxidation of the resulting alkylradical intermediates, followed by hydrolysis, provides expedient access to ketones and esters. By modification of the alcohol solvent, different alkyl ester products may be obtained. The method is compatible with a number of functional groups including alkenyl halides, sulfides, triflates, and phosphonates and provides a mild and practical alternative to the Tamao-Fleming oxidation of vinylsilanes and the Arndt-Eistert homologation.
- Ma, Xiaoshen,Herzon, Seth B.
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p. 8673 - 8695
(2016/10/17)
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- Direct Transformation of Ethylarenes into Primary Aromatic Amides with N -Bromosuccinimide and I2-Aqueous NH3
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A variety of ethylarenes were converted into the corresponding primary aromatic amides in good yields via treatment with N-bromosuccinimide in the presence of a catalytic amount of 2,2′-azobis(isobutyronitrile) in a mixture of ethyl acetate and water, acetonitrile and water, or chloroform and water, followed by reaction with molecular iodine and aq NH3 in one pot. It was found that aryl α-bromomethyl ketones and/or aryl methyl ketones were formed at the first reaction step and their iodoform-type reaction occurred at the second reaction step to provide primary aromatic amides. The present reaction is a useful and practical transition-metal-free method for the preparation of primary aromatic amides from ethylarenes. (Chemical Equation Presented).
- Shimokawa, Shohei,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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supporting information
p. 784 - 787
(2016/03/01)
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- Metal-Free Markovnikov-Type Alkyne Hydration under Mild Conditions
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A Markovnikov-type alkyne hydration protocol is presented using 20% CF3SO3H (TfOH) as the catalyst under unprecedented mild conditions applicable to various alkynes, including terminal arylalkynes, terminal nonfunctionalized aliphatic alkynes, and internal alkynes with excellent regioselectivity in good to excellent yields (average yields >85%). The reaction procedure operates under mild conditions (25-70°C), with broad functional group compatibility, and uses only slightly more than a stoichiometric amount of water in the absence of any transition metal. The success of this protocol hinges upon the utilization of trifluoroethanol as the solvent.
- Liu, Wenbo,Wang, Haining,Li, Chao-Jun
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supporting information
p. 2184 - 2187
(2016/06/01)
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- SELECTIVE OCTAHYDRO-CYCLOPENTA[C] PYRROLE NEGATIVE MODULATORS OF NR2B
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Compounds that selectively negatively modulate NMDA receptors containing an NR1/NR2B subunit, pharmaceutical compositions comprising the compounds, and methods of treating a disease using the compounds are disclosed. Such diseases include, without limitation, neurological dysfunction such as Parkinson's disease, Huntington's disease, amyotrophic lateral sclerosis, multiple sclerosis, and seizure disorders; emotional disorders; depression; bipolar disorder; obsessive-compulsive disorder; and other anxiety disorders.
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Paragraph 0154
(2015/04/15)
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- Palladium nanoparticles immobilized on magnetic nanoparticles: An efficient semi-heterogeneous catalyst for carbonylation of aryl bromides
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We describe a method for supporting palladium nanoparticles on magnetic nanoparticles modified with amino-functionalized dihydro-imidazolium groups. This catalytic system is very efficient in alkoxy- and amino-carbonylation reactions of aryl bromides. The catalyst can be easily recovered from the reaction mixture by applying an external magnetic field and reused for over five consecutive cycles without a significant decrease in its activity.
- Dutta, Bishnu,Omar, Suheir,Natour, Suzana,Abu-Reziq, Raed
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- Aerobic Copper-Catalyzed O-Methylation with Methylboronic Acid
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The oxidative coupling of alkylboronic acids with oxygen nucleophiles offers a strategy for replacing toxic, electrophilic alkylating reagents. Although the Chan-Lam reaction has been widely applied in the arylation of heteroatom nucleophiles, O-alkylation with boronic acids is rare. We report a Cu-catalyzed nondecarboxylative methylation of carboxylic acids with methylboronic acid that proceeds in air with no additional oxidant. An isotope-labeling study supports an oxidative cross-coupling mechanism, in analogy to that proposed for Chan-Lam arylation.
- Jacobson, Clare E.,Martinez-Mu?oz, Noelia,Gorin, David J.
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p. 7305 - 7310
(2015/07/28)
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- A Single Nickel Catalyst for the Acceptorless Dehydrogenation of Alcohols and Hydrogenation of Carbonyl Compounds
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A single homogeneous nickel(II) complex, supported by the tris(3,5-dimethylpyrazolyl)borate ligand and 2-hydroxyquinoline ancillary ligand, is shown to catalyze both acceptorless dehydrogenation of alcohols and hydrogenation of carbonyl compounds under mild conditions. Products from the catalytic reactions were isolated with good yields. A mechanistic investigation highlights the critical role of the 2-hydroxyquinoline ligand in the catalysis and argues against a stepwise dehydrogenation pathway.
- Chakraborty, Sumit,Piszel, Paige E.,Brennessel, William W.,Jones, William D.
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supporting information
p. 5203 - 5206
(2015/11/18)
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- Nitrogen enriched mesoporous organic polymer anchored copper(ii) material: An efficient and reusable catalyst for the synthesis of esters and amides from aromatic systems
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A new copper-grafted mesoporous poly-melamine-formaldehyde (Cu-mPMF) has been synthesized from melamine and paraformaldehyde in DMSO medium, followed by grafting of Cu(ii) at its surface. Cu-mPMF has been characterized by elemental analysis, powder XRD, HR TEM, FE-SEM, N2 adsorption study, FT-IR, UV-vis DRS, TGA-DTA, EPR spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The Cu-grafted mesoporous material showed very good catalytic activity in methyl esterification of benzylic alcohols and amidation of nitriles. Moreover, the catalyst is easily recoverable and can be reused seven times without appreciable loss of catalytic activity in the above reactions. The highly dispersed and strongly bound Cu(ii) sites in the Cu-grafted mesoporous polymer could be responsible for the observed high activities of the Cu-mPMF catalyst. Due to strong binding with the functional groups of the polymer, no evidence of leached copper from the catalyst during the course of reaction emerged, suggesting true heterogeneity in the catalytic process. This journal is
- Molla, Rostam Ali,Iqubal, Md. Asif,Ghosh, Kajari,Kamaluddin,Islam, Sk. Manirul
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p. 6546 - 6559
(2015/04/14)
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- Well-defined iron catalysts for the acceptorless reversible dehydrogenation-hydrogenation of alcohols and ketones
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Acceptorless dehydrogenation of alcohols, an important organic transformation, was accomplished with well-defined and inexpensive iron-based catalysts supported by a cooperating PNP pincer ligand. Benzylic and aliphatic secondary alcohols were dehydrogenated to the corresponding ketones in good isolated yields upon release of dihydrogen. Primary alcohols were dehydrogenated to esters and lactones, respectively. Mixed primary/secondary diols were oxidized at the secondary alcohol moiety with good chemoselectivity. The mechanism of the reaction was investigated using both experiment and DFT calculations, and the crucial role of metal-ligand cooperativity in the reaction was elucidated. The iron complexes are also excellent catalysts for the hydrogenation of challenging ketone substrates at ambient temperature under mild H2 pressure, the reverse of secondary alcohol dehydrogenation.
- Chakraborty, Sumit,Lagaditis, Paraskevi O.,F?rster, Moritz,Bielinski, Elizabeth A.,Hazari, Nilay,Holthausen, Max C.,Jones, William D.,Schneider, Sven
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p. 3994 - 4003
(2015/01/16)
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- Copper-catalyzed decarboxylative methylation of aromatic carboxylic acids with PhI(OAc)2
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The copper-catalyzed decarboxylative methylation of aromatic carboxylic acids was developed by using PhI(OAc)2 to provide a new strategy for the methylation of aryl acids through the decarboxylation of alkyl acids. The mechanism and the roles of each reactant in the reaction were investigated extensively. Copyright
- Jiang, Yuyu,Pan, Shulei,Zhang, Yanghui,Yu, Jingxun,Liu, Hongqiang
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supporting information
p. 2027 - 2031
(2014/04/17)
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- Ruthenium-catalyzed oxidative kinetic resolution of unactivated and activated secondary alcohols with air as the hydrogen acceptor at room temperature
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Enantiopure alcohols are versatile building blocks for asymmetric synthesis and the kinetic resolution (KR) of racemic alcohols is a reliable method for preparing them. Although many KR methods have been developed, oxidative kinetic resolution (OKR), in which dioxygen is used as the hydrogen acceptor, is the most atom-efficient. Dioxygen is ubiquitous in air, which is abundant and safe to handle. Therefore, OKR with air has been intensively investigated and the OKR of benzylic alcohols was recently achieved by using an Ir catalyst without any adjuvant. However, the OKR of unactivated alcohols remains a challenge. An [(aqua)Ru(salen)] catalyzed OKR with air as the hydrogen acceptor was developed, in which the aqua ligand is exchanged with alcohol and the Ru complex undergoes single electron transfer to dioxygen and subsequent alcohol oxidation. This OKR can be applied without any adjuvant to activated and unactivated alcohols with good to high enantioselectivity. The unique influence of substrate inhibition on the enantioselectivity of the OKR is also described. Alcohol resolution: An (aqua)ruthenium salen complex catalyzes the efficient oxidative kinetic resolution of both activated and unactivated secondary alcohols with air as the hydrogen acceptor at room temperature. The reaction is compatible with various functional groups, including halogen, ether, silyl ether, and ester groups. The reaction rate is lower at higher substrate concentrations as a result of substrate inhibition.
- Mizoguchi, Hirotaka,Uchida, Tatsuya,Katsuki, Tsutomu
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supporting information
p. 3178 - 3182
(2014/04/03)
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- One-pot formal synthesis of biorenewable terephthalic acid from methyl coumalate and methyl pyruvate
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Diverse functionalized aromatic compounds are constructed from captodative dienophiles with exclusive regioselectivity. 100% biorenewable dimethyl terephthalate (DMT) from methyl coumalate and methyl pyruvate is achieved in a one-pot, Diels-Alder/decarboxylation/elimination sequence in nearly quantitative yield. The DMT system is solvent-free and purification is accomplished through recrystallization. DMT hydrolysis reveals the co-monomer terephthalic acid (TPA) as a bio-based drop-in replacement for the polymer industry, avoiding harsh oxidation and petrochemicals. the Partner Organisations 2014.
- Lee, Jennifer J.,Kraus, George A.
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supporting information
p. 2111 - 2116
(2014/04/17)
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- Electrocarboxylation of haloacetophenones at silver electrode
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Electrocarboxylation of haloacetophenones 1 has been carried out in an undivided cell equipped with silver cathode and Mg sacrificial anode in N,N-dimethylformamide. The electroreduction behavior of these haloacetophenones at the Ag electrode was investig
- Wang, Huan,Xu, Xiao-Ming,Lan, Yang-Chun,Wang, Hui-Mei,Lu, Jia-Xing
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p. 1140 - 1143
(2014/02/14)
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- Zinc-acetic acid promoted reductive carbon-nitrogen bond cleavage reaction of α-aminoketones
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Scope and limitation of the reductive cleavage reaction of α-aminoketone systems with zinc-acetic acid are described. The carbon-nitrogen bond cleavage reaction was applicable to a wide range of α-aminoalkyl aryl ketones possessing various substituents on the aromatic ring. In contrast, α-aminoalkyl alkyl ketones with protons at the α'-position or α-aminoesters were sluggish to the carbon-nitrogen cleavage reaction.
- Ishikawa, Kyoko,Tomatsu, Miyuki,Nagase, Hiroshi,Fujii, Hideaki
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p. 1051 - 1063
(2014/01/17)
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