- 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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p. 17887 - 17896
(2020/08/19)
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- Sodium pyruvate as a peroxide scavenger in aerobic oxidation under carbene catalysis
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NHC-Catalyzed aerobic oxidative reactions of imines and aldehydes have been developed by using sodium pyruvate as a novel and efficient peroxide scavenger. A structurally diverse set of imidates and amidines has been prepared from imines using this strategy. This general and efficient strategy features the use of sodium pyruvate as a novel and efficient peroxide scavenger and ambient air as the sole oxidant to efficiently control the NHC-catalyzed aerobic reaction pathway (selective realization of the oxidative pathway) under mild and green conditions. This journal is
- Fu, Zhenqian,Hong, Xianfang,Huang, Wei,Wang, Guanjie,Wei, Chenlong
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supporting information
p. 6819 - 6826
(2020/11/09)
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- Method for preparing carboxylic ester by alcohol direct oxidation esterification method
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The invention discloses a method for preparing a carboxylic ester by an alcohol direct oxidation esterification method. The method comprises the following steps: taking an aromatic alcohol compound ora saturated linear aliphatic alcohol as a reaction substrate, taking an Au-Co composite particle carrier as a catalyst, adding a low catalytic amount of alkali, reacting for 0.5-15 h in a methanol solvent at the temperature of 25-150 DEG C in air or oxygen or a mixed atmosphere of the air or the oxygen, and performing aftertreatment to obtain a target product carboxylic ester. According to the preparation method disclosed by the invention, the process steps are reduced, conditions are mild, catalyst consumption is less, atom economy is high, the method is simple to operate, the application range of the substrate is wide, and industrial practicability is achieved.
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Paragraph 0042; 0043
(2019/06/30)
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- Synthesis and characterization of an A2BC type phthalocyanine and its visible-light-responsive photocatalytic H2 production performance on graphitic carbon nitride
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A highly asymmetric A2BC type zinc phthalocyanine (Zn-di-PcNcTh) has been designed and synthesized. The Zn-di-PcNcTh used a π electron rich thiophene ring in place of the benzenoid rings of phthalocyanine which acted as an electron donor, diphenylphenoxy substituents to retard aggregation and a carboxyl-naphthalene unit as an electron acceptor. The asymmetric phthalocyanine shows a strongly split Q-band and wide spectral absorption in the visible/near-IR light region, which can extend the spectral response region of graphitic carbon nitride (g-C3N4) from ~450 nm to more than 800 nm. By using it as a sensitizer of 1.0 wt% Pt-loaded graphitic carbon nitride (g-C3N4), the experimental results indicate that Zn-di-PcNcTh-Pt/g-C3N4 shows a H2 production efficiency of 249 μmol h-1 with an impressive turnover number (TON) of 9960.8 h-1 under visible light (λ ≥ 420 nm) irradiation, much higher than that of pristine Pt/g-C3N4. Owing to the introduction of a highly bathochromic shift of 3,4-dicyanothiophene and the valuable "push-pull" effect from the thiophene (electron donor) to the carboxyl-naphthalene (electron acceptor) unit, Zn-di-PcNcTh/g-C3N4 gives an extremely high apparent quantum yield (AQY) of 2.44%, 3.05%, and 1.53% under 700, 730, and 800 nm monochromatic light irradiation, respectively, under optimized photocatalytic conditions.
- Guo, Yingying,Song, Shuaishuai,Zheng, Ya,Li, Renjie,Peng, Tianyou
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supporting information
p. 14071 - 14079
(2016/11/05)
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- Direct oxidative esterification of alcohols and hydration of nitriles catalyzed by a reusable silver nanoparticle grafted onto mesoporous polymelamine formaldehyde (AgNPs@mPMF)
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A nitrogen-rich mesoporous organic polymer was synthesized as a novel support. A silver nanoparticle was synthesized and grafted onto it. The prepared catalyst (AgNPs@mPMF) was characterized by powder X-ray diffraction (XRD), scanning electron microscopy(SEM) and energy dispersive X-ray spectrometry (EDS), thermogravimetric analysis (TGA), high-resolution transmission electron microscopy (HRTEM), UV-vis diffuse reflectance spectroscopy (DRS), N2 adsorption, Raman spectroscopy and EPR study. The catalytic activity was evaluated for the oxidative esterification reaction of alcohols and hydration of nitriles. The oxidative esterification reaction was carried out for various activated alcohols giving excellent yields of the corresponding ester products. The catalyst was also efficient in the hydration of nitriles. Both reactions were optimized by varying the bases, temperatures and solvents. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity and selectivity.
- Ghosh, Kajari,Iqubal, Md. Asif,Molla, Rostam Ali,Mishra, Ashutosh,Kamaluddin,Islam, Sk Manirul
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p. 1606 - 1622
(2015/04/27)
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- Upgrading malic acid to bio-based benzoates via a Diels-Alder-initiated sequence with the methyl coumalate platform
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The conversion of naturally-occurring malic acid to the 2-pyrone methyl coumalate was optimized using a variety of acid catalysts. Coupling methyl coumalate with electron-rich dienophiles in an inverse electron-demand Diels-Alder (IEDDA)/decarboxylation/elimination domino sequence resulted in an investigation of the scope and limitations of the methodology. The thermal, metal-free, and one-pot procedure allows regioselective access to diverse aromatic compounds including tricyclic, biphenyl, and pyridinyl systems for elaboration. A comparison with analogous pyrones demonstrates the striking efficacy of methyl coumalate as a versatile platform for the generation of biorenewable functionalized benzoates. This journal is
- Lee, Jennifer J.,Pollock Iii, Gerald R.,Mitchell, Donald,Kasuga, Lindsay,Kraus, George A.
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p. 45657 - 45664
(2015/02/19)
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- Facile and efficient gold-catalyzed aerobic oxidative esterification of activated alcohols
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A facile and efficient methodology is presented for the direct oxidative esterification of alcohols with alcohols catalyzed by NaAuCl4. Just in the presence of a low catalytic amount of base additive, the newly developed catalytic system proceeds with high selectivity and broad substrate scope under mild conditions with dioxygen or air as the environmentally benign terminal oxidant. Various alcohols including benzylic and allylic alcohols were smoothly reacted with methanol and even with long-chain aliphatic alcohols, affording the desired products in good to excellent yields (up to 95% yield). The present system showed high catalytic activity with a TOF up to 219 h-1. Kinetic studies of the reaction process provide fundamental insights into the catalytic pathway, and a possible reaction pathway was proposed based on the results of the control experiments. XPS, TEM, and UV-vis were carried out to characterize the chemical state of the Au catalyst in the present catalytic system. The results indicate that the Au nanoparticles were generated in situ and supported on K2CO3, forming a simple, recyclable and selective catalyst system for the direct oxidative esterification of alcohols. the Partner Organisations 2014.
- Wang, Lianyue,Li, Jun,Dai, Wen,Lv, Ying,Zhang, Yi,Gao, Shuang
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p. 2164 - 2173
(2014/04/17)
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- Oxidation of benzaldehydes to benzoate esters using household bleach and sodium iodide in alcohol solvents
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Various substituted benzaldehydes were converted into benzoate esters with household bleach and sodium iodide in an alcohol solvent. The reaction works best with methanol. Only 4-chlorobenzaldehyde, 3-nitrobenzaldehyde, and 4-nitrobenzaldehyde reacted completely with 1-propanol under these conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
- Hathaway, Bruce A.,Dekastle, Christopher A. D.,Arnett, Brianna A.
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supporting information
p. 660 - 664
(2014/01/17)
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- Alkylation of substituted benzoic acids in a continuous flow microfluidic microreactor: Kinetics and linear free energy relationships
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Alkylation of para-substituted benzoic acids by iodomethane using an organic superbase, 1,8-bis(tetramethylguanidino)naphthalene (TMGN) in DMF was chosen as a model reaction to test the quality of the control of experimental parameters in a continuous flow microfluidic reactor as it is expected to follow a perfect second order kinetics with a large dynamics by varying the substituents. These conditions may be directly used for the synthesis of natural product esters. Because TMGN reacts slowly with iodomethane, the three different mixing strategies between substrate, base and alkylating reagent were compared. The rate constants were determined for the reaction with a set of alkylating agents and in different solvents. In order to test the quality of the obtained data, temperature effect and free energy relationships, which are expected to follow predictable laws, were investigated. The kinetics vary over 6 orders of magnitude and follows a perfect Arrhenius law, allowing the determination of the energies, enthalpies, and entropies of activation. Finally, we established a Hammett linear relationship for a series of 16 substituted benzoic acids, leading to a reaction constant ρ of -0.65 for this reaction. The quality of the obtained kinetics allowed us to discuss the outliers. All kinetics were obtained with less than 0.5 mmol of substrate.
- Gholamipour-Shirazi, Azarmidokht,Rolando, Christian
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experimental part
p. 811 - 818
(2012/08/07)
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- Discovery of (2,4-Dihydroxy-5-isopropylphenyl)-[5-(4-methylpiperazin-1- ylmethyl)-1,3-dihydroisoindol-2-yl]methanone (AT13387), a novel inhibitor of the molecular chaperone Hsp90 by fragment based drug design
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Inhibitors of the molecular chaperone heat shock protein 90 (Hsp90) are currently generating significant interest in clinical development as potential treatments for cancer. In a preceding publication (DOI: 10.1021/jm100059d) we describe Astex's approach to screening fragments against Hsp90 and the subsequent optimization of two hits into leads with inhibitory activities in the low nanomolar range. This paper describes the structure guided optimization of the 2,4-dihydroxybenzamide lead molecule 1 and details some of the drug discovery strategies employed in the identification of AT13387 (35), which has progressed through preclinical development and is currently being tested in man.
- Woodhead, Andrew J.,Angove, Hayley,Carr, Maria G.,Chessari, Gianni,Congreve, Miles,Coyle, Joseph E.,Cosme, Jose,Graham, Brent,Day, Philip J.,Downham, Robert,Fazal, Lynsey,Feltell, Ruth,Figueroa, Eva,Frederickson, Martyn,Lewis, Jonathan,McMenamin, Rachel,Murray, Christopher W.,O'Brien, M. Alistair,Parra, Lina,Patel, Sahil,Phillips, Theresa,Rees, David C.,Rich, Sharna,Smith, Donna-Michelle,Trewartha, Gary,Vinkovic, Mladen,Williams, Brian,Woolford, Alison J.-A.
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supporting information; experimental part
p. 5956 - 5969
(2010/11/04)
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- Substituted Spiroamide Compounds
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Substituted spiroamide compounds corresponding to formula (I): wherein A, B, Q1, Q2, Q3, Q4, R1, R8, R9a, R9b, R12, R13, R200 and R210 have defined meanings, processes for their preparation, pharmaceutical compositions containing such compounds, and the use of such compounds for treating or inhibiting pain or other conditions mediated at least in part by the bradykinin 1 receptor (B1R).
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Page/Page column 20
(2010/09/18)
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- Computational and experimental structure-reactivity relationships: evidence for a side reaction in Alpine-Borane reductions of d-benzaldehydes
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Extraordinary stereoselectivity, approaching 100%, has been reported in the reductions of d-benzaldehydes by B-isopinocampheyl-9-borabicyclo[3.3.1]nonane (Alpine-Borane). This is likely because of the extreme size disparity of groups on either side of the carbonyl. Here, we present a structure-reactivity study whereby the reductions of variably substituted d-benzaldehydes are explored using highly sensitive measures for enantiomeric excess and relative reactivity. These results are compared to the relative rates predicted from density functional calculations. The results indicate that 2,6-disubstitution adversely affects the stereoselectivity by means of a non-selective reduction via the dehydroboration product of Alpine-Borane, 9-borabicyclo[3.3.1]nonane.
- Zhu, Hui,Soledad Reyes,Meyer, Matthew P.
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supporting information; experimental part
p. 6803 - 6806
(2010/04/29)
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- Selective oxidation of acetophenones bearing various functional groups to benzoic acid derivatives with molecular oxygen
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Acetophenones substituted by alkyl, alkoxy, acetoxy, and halogen groups were selectively oxidized with molecular oxygen to the corresponding benzoic acids by using the N,N',N"-trihydroxyisocyanuric acid (THICA)/cobalt(II) acetate [Co(OAc)2] and THICA/Co(OAc)2/manganese(II) acetate.
- Nakamura, Ryota,Obora, Yasushi,Ishii, Yasutaka
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experimental part
p. 1677 - 1684
(2011/02/25)
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- Inhibitors of phenylalanine ammonialyase: 1-aminobenzylphosphonic acids substituted in the benzene ring
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Dextrorotatory 1-amino-3′,4′-dichlorobenzylphosphonic acid was found to be a potent inhibitor of the plant enzyme phenylalanine ammonia-lyase both in vitro and in vivo from among the ring-substituted 1-aminobenzylphosphonic acids and other analogues of phenylglycine. A structure activity relationship analysis of the results obtained permits predictions on the geometry of the pocket of the enzyme and is a basis in the strategy of better inhibitor synthesis.
- Zoń, Jerzy,Amrhein, Nikolaus,Gancarz, Roman
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- Antiviral agent containing benzodithiin derivative as active ingredient
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Antiviral agents comprising, as an active ingredient, a 1,4-dihydro-2,3-benzodithiin derivative of the formula STR1 wherein each symbol is as defined in the Specification, or a pharmacologically acceptable salt thereof. The antiviral agents of the present invention have superior antiviral activity and are effective for the preventive and therapeutic treatment of viral diseases caused typically by RS virus.
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- Aromatic Spiranes XX [1]: Syntheses of Dimethylsubstituted 2-Carboxymethyl-indan-1-ones and Benzylchlorides as Synthones for Syntheses of di- to tetramethylsubstituted Spirobiindandiones
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The isomeric dimethyl methylbenzoates 5, obtained from the bromides via Grignard reactions with dimethylcarbonate, were reduced with LiAlH4 to the hydroxymethyl derivatives 6. The latter were then transformed both to the benzylchlorides 7 (with SOCl2) and to the aldehydes 8 (with pyridinium chlorochromate). Knoevenagel-Doebner reaction of 8 afforded the acrylic acids 9 which (after hydrogenation to 11) were cyclized to the desired indanones 12 with polyphosphoric acid. On the other hand, 12c and 12e were prepared from dimethyl 3-chloropropiophenone (14) by warming with sulfuric acid. After NaH-catalyzed reaction with dimethylcarbonate, the indanones 12 gave the ketoesters 15 which then could be hydrogenated to the indanes 16. All reactions proceeded with satisfactory to excellent yields (60-90%).
- Neudeck
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p. 185 - 200
(2007/10/03)
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- Isoindoline derivative
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Isoindoline derivatives represented by the formula (I) and their salts are disclosed. STR1 There are many varieties for the compound depending on the types of residues R1 -R9 and X. The compounds can be prepared from quinoline derivatives of the formula (II) and an isoindoline derivatives of the formula (III). The compounds of formula (I) and their salts have excellent antibacterial activities against both gram positive and gram negative microorganisms. They can be used as a medicine, an agrichemical, and a food preservative.
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- NMR studies of bond order in distorted aromatic systems
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The 4JH-C=C-Me coupling constant has been previously established1,2 as a probe of bond order. This has now been used to examine the bond orders of compounds containing severely distorted benzene nuclei. In the case of 3,4-di-tert-butyltoluene, no electronic distortions in the aromatic ring can be detected by this method. A series of moderately to severely distorted paracyclophanes show no perturbation of electronic structure, with the possible exception of 8-methyl[6]paracyclophane, which exhibits a barely significant deviation from unstrained values. These conclusions are supported by the results of SCF-MO calculations.
- Gready, Jill E.,Hambley, Trevor W.,Kakiuchi, Kiyomi,Kobiro, Kazuya,Sternhell, Sever,Tansey, Charles W.,Tobe, Yoshito
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p. 7537 - 7540
(2007/10/02)
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- 5- or 6-alkoxycarbonyl-2,3-dicyanonaphthalenes
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A 5- or 6-alkoxycarbonyl-2,3-dicyanonaphthalene is a useful intermediate for synthesizing a tetrakis(alkoxycarbonyl) metal naphthalocyanine.
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- Naphthalocyanine derivatives and production processes thereof, as well as optical information recording media using the derivatives and production processes thereof
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There are disclosed a novel naphthalocyanine derivative represented by the general formula [I] or [II] shown below, a process for preparing said derivative, an optical information recording medium using said deriva-tive, and a process for preparing thereo
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