Synthesis, crystal structure of Co(II)(6-methoxybenzothiazole-2-carboxylate)2(DMF)2 and its application to carbonylation of benzyl chloride

Zhang, Bin,Li, Jianli,Chen, Wei,Wang, Yunxia,Shi, Zhen

, p. 111 - 114 (2010)

A new complex, Co(MBTC)2(DMF)2 (MBTC(6-methoxybenzothiazole-2-carboxylate, DMF=N,N-dimethylformamide), was synthesized in DMF solution and characterized by single crystal X-ray diffraction analysis. Using the cobalt complex as catalyst, phenylacetic acid was prepared by the carbonylation of benzyl chloride with carbon monoxide (0.1 MPa). The effects of solvents, phase transfer catalysts and temperature on the reactions were investigated. The yield of phenylacetic acid was higher than 90% in optimized condition.

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Wenkert,E.,McPherson,C.A.

, p. 8084 - 8090 (1972)

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Penicillin G amidase-catalysed hydrolysis of phenylacetic hydrazides on a solid phase: A new route to enzyme-cleavable linkers

Basso, Alessandra,Ebert, Cynthia,Gardossi, Lucia,Linda, Paolo,Phuong, Thao Tran,Zhu, Mingzhao,Wessjohann, Ludger

, p. 963 - 966 (2005)

A novel catalytic property of penicillin G amidase (PGA) is described. Unexpectedly, the enzyme can hydrolyse hydrazide bonds with good efficiency, and in solution the enzyme shows a selectivity that is similar to phenylacetamides. The hydrolysis of phenylacetic hydrazides releases hydrazine, but no inhibition due to the formation of such reactive compounds was observed. This novel catalytic property was assayed also on a solid phase as a pioneering route for the design of enzyme-cleavable linkers and masked scavengers for ketones. On a solid phase a phenylacetic hydrazide compound was chemically synthesised on PEGA1900 and PEGA+ (two co-polymers of acrylamide and ethylene glycol) and the efficiency of PGA in the release of phenylacetic acid depended on the diffusion of the protein inside the polymer. On PEGA+ the enzyme, as previously described, shows a good diffusion due to an improved electrostatic interaction with PGA thus achieving good hydrolytic conversions.

Copper-catalysed Reaction of Arylacetylenes with C,N-Diarylnitrones

Okuro, Kazumi,Enna, Masahiro,Miura, Masahiro,Nomura, Masakatsu

, p. 1107 - 1108 (1993)

Reaction of arylacetylenes with C,N-diarylnitrones is effectively catalysed by copper(I) iodide-dppe in the presence of potassium carbonate to give the corresponding 1-azabut-1-en-3-yne (iminopropyne) derivatives in good yield.

Cornforth

, p. 3933 (1974)

Oxygen-Atom Transfer from Iodosobenzene to Ketenes, α-Keto Carboxylic Acids, and Ketones

Moriarty, Robert M.,Gupta, Satish C.,Hu, Henry,Berenschot, Daniel M.,White, Kenneth B.

, p. 686 - 688 (1981)

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Bryce-Smith

, p. 1079,1080, 1084 (1954)

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Relative activity of metal cathodes towards electroorganic coupling of CO2 with benzylic halides

Engelhardt, Helen,Klinkova, Anna,Medvedev, Jury J.,Medvedeva, Xenia V.

, (2021)

Electrochemical reduction of benzylic halides represents a convenient route to generating carbanions for their subsequent coupling with CO2 to obtain various carboxylic acids. Despite the industrial prospects of this synthetic process, it still lacks systematic studies of the efficient catalysts and reaction media design. In this work, we performed a detailed analysis of the catalytic activity of a series of different metal electrodes towards electroreduction of benzylic halides to corresponding radicals and carbanions using cyclic voltammetry. Specifically, we screened and summarized the performance of 12 bulk metal cathodes (Ag, Au, Cu, Pd, Pt, Ni, Ti, Zn, Fe, Al, Sn, and Pb) and 3 carbon-based materials (glassy carbon, carbon cloth, and carbon paper) towards electrocarboxylation of eight different benzylic halides and compare it to direct CO2 reduction in acetonitrile. Extensive experimental studies along with a detailed analysis of the results allowed us to map specific electrochemical properties of different metal electrodes, i.e., the potential zones related to the one- and two-electron reduction of organic halides as well as the potential windows where the electrochemical activation of CO2 does not occur. The reported systematic analysis should facilitate the development of nanostructured electrodes based on group 10 and 11 transition metals to further optimize the efficiency of electrocarboxylation of halides bearing specific substituents and make this technology competitive to current synthetic methods for the synthesis of carboxylic acids.

Synthesis of Phenylacetic Acid via Carbonylation of Benzyl Chloride in the Presence of a Water-Soluble Complex, 2>, and Surfactants under Two-Phase Conditions

Okano, Tamon,Hayashi, Tetsuji,Kiji, Jitsuo

, p. 2339 - 2341 (1994)

The addition of surfactants such as n-C7H15SO3Na or n-C7H15COONa is effective in acceleration of the carboxylation of benzyl chloride using a water-soluble catalyst, 2>, in an aqueous NaOH-heptane solution.Phenylacetic acid is easily isolated from the aqueous layer in high yields.However, the addition of n-C7H15SO3Na has no effect on the carboxylation using hydrophobic catalysts, and , under the two phase conditions.

The combi-CLEA approach: Enzymatic cascade synthesis of enantiomerically pure (S)-mandelic acid

Chmura, Andrzej,Rustler, Sven,Paravidino, Monica,Van Rantwijk, Fred,Stolz, Andreas,Sheldon, Roger A.

, p. 1225 - 1232 (2013)

Enantiomerically pure (S)-mandelic acid was synthesised from benzaldehyde by sequential hydrocyanation and hydrolysis in a bienzymatic cascade at starting concentrations up to 0.25 M. A cross-linked enzyme aggregate (CLEA) composed of the (S)-selective oxynitrilase from Manihot esculenta and the non-selective nitrilase from Pseudomonas fluorescens EBC 191 was employed as the biocatalyst. The nitrilase produces approx. equal amounts of (S)-mandelic acid and (S)-mandelic amide from (S)-mandelonitrile under standard conditions, but we surprisingly found that high (up to 0.5 M) concentrations of HCN induced a marked drift towards amide production. By including the amidase from Rhodococcus erythopolis in the CLEA we obtained (S)-mandelic acid as the sole product in 90% yield and >99% enantiomeric purity.

A recyclable, metal-free mechanochemical approach for the oxidation of alcohols to carboxylic acids

Carr, Preston,Denlinger, Kendra Leahy,Mack, James,Waddell, Daniel C.

, (2020)

The oxidation of primary alcohols under mechanochemical conditions in a Spex8000M Mixer/Mill was investigated. To facilitate ease of separation and recyclability, a polystyrene-bound version of a TEMPO catalyst was employed. When paired with Oxone in a stainless-steel vial with a stainless-steel ball, several primary alcohols were successfully oxidized to the corresponding carboxylic acids. The product was isolated using gravity filtration, which also allowed for the polystyrene-bound TEMPO catalyst to be recovered and reused in subsequent oxidation reactions. Furthermore, it was demonstrated that the size and steric hindrance of the primary alcohol does not hinder the rate of the reaction. Finally, the aldehyde was selectively obtained from a primary alcohol under ball milling conditions by using a combination of non-supported TEMPO with a copper vial and copper ball.

Efficient Assay for the Detection of Hydrogen Peroxide by Estimating Enzyme Promiscuous Activity in the Perhydrolysis Reaction

Wilk, Monika,Ostaszewski, Ryszard

, p. 1464 - 1469 (2021)

Hydrogen peroxide is an ideal oxidant in view of its availability, atom economy, or green aspects. Furthermore, it is produced by the cell mitochondria and plays a meaningful role in controlling physiological processes, but its unregulated production leads to the destruction of organs. Due to its diverse roles, a fast and selective method for hydrogen peroxide detection is the major limitation to preventing the negative effects caused by its excess. Therefore, we aimed to develop an efficient assay for the detection of H2O2. For this purpose, we combined the enzymatic method for the detection of hydrogen peroxide with the estimation of the promiscuity of various enzymes. We estimated the activity of an enzyme in the reaction of p-nitrophenyl esters with hydrogen peroxide resulting in the formation of peracid. To our knowledge, there is no example of a simple, multi-sensor demonstrating the promiscuous activity of an enzyme and detecting hydrogen peroxide in aqueous media.

Site-selective immobilisation of functional enzymes on to polystyrene nanoparticles

Wong, Lu Shin,Okrasa, Krzysztof,MicKlefield, Jason

, p. 782 - 787 (2010)

The immobilisation of proteins on to nanoparticles has a number of applications ranging from biocatalysis through to cellular delivery of biopharmaceuticals. Here we describe a phosphopantetheinyl transferase (Sfp)-catalysed method for immobilising proteins bearing a small 12-mer "ybbR" tag on to nanoparticles functionalised with coenzyme A. The Sfp-catalysed immobilisation of proteins on to nanoparticles is a highly efficient, single step reaction that proceeds under mild conditions and results in a homogeneous population of proteins that are covalently and site-specifically attached to the surface of the nanoparticles. Several enzymes of interest for biocatalysis, including an arylmalonate decarboxylase (AMDase) and a glutamate racemase (GluR), were immobilised on to nanoparticles using this approach. These enzymes retained their activity and showed high operational stability upon immobilisation. The Royal Society of Chemistry 2010.

Brown,Darwent

, p. 169 (1979)

A simple and efficient protocol for the deprenylation of ethers and esters catalysed by zirconium(IV) chloride-sodium iodide

Sharma, Gangavaram V. M.,Reddy, Ch. Govardhan,Krishna, Palakodety Radha

, p. 1728 - 1730 (2003)

An efficient protocol for the deprotection of prenyl ethers and esters is developed using 20 mol% ZrCl4-NaI (1:1) in CH3CN as a reagent system. A variety of substrates as well as functional groups well tolerate the present reaction conditions.

Isolation of 2-Alkyl-4-quinolones with Unusual Side Chains from a Chinese Pseudomonas aeruginosa Isolate

Li, Jianye,Sun, Weiwei,Saalim, Muhammad,Wei, Guixiang,Zaleta-Pinet, Diana A.,Clark, Benjamin R.

, p. 2294 - 2298 (2020)

Chemical investigation of a Pseudomonas aeruginosa strain isolated from Hebei, China, led to the isolation of a suite of quinolones, quinolone-N-oxides, and phenazines, the structures of which were elucidated by detailed spectroscopic analysis. Most notable among the secondary metabolites isolated was an unprecedented 4-quinolone containing an S-methyl group in the side chain and a new derivative including a phenyl ring in the side chain, which expand significantly the variety of structural motifs found in the quinolones and raise interesting questions about their biosynthesis.

Alper,Des Abbayes

, p. C11,C12-C14 (1977)

Cassar,Foa

, p. C15 (1977)

Design and evolution of an enzyme with a non-canonical organocatalytic mechanism

Burke, Ashleigh J.,Lovelock, Sarah L.,Frese, Amina,Crawshaw, Rebecca,Ortmayer, Mary,Dunstan, Mark,Levy, Colin,Green, Anthony P.

, p. 219 - 223 (2019)

The combination of computational design and laboratory evolution is a powerful and potentially versatile strategy for the development of enzymes with new functions1–4. However, the limited functionality presented by the genetic code restricts the range of catalytic mechanisms that are accessible in designed active sites. Inspired by mechanistic strategies from small-molecule organocatalysis5, here we report the generation of a hydrolytic enzyme that uses Nδ-methylhistidine as a non-canonical catalytic nucleophile. Histidine methylation is essential for catalytic function because it prevents the formation of unreactive acyl-enzyme intermediates, which has been a long-standing challenge when using canonical nucleophiles in enzyme design6–10. Enzyme performance was optimized using directed evolution protocols adapted to an expanded genetic code, affording a biocatalyst capable of accelerating ester hydrolysis with greater than 9,000-fold increased efficiency over free Nδ-methylhistidine in solution. Crystallographic snapshots along the evolutionary trajectory highlight the catalytic devices that are responsible for this increase in efficiency. Nδ-methylhistidine can be considered to be a genetically encodable surrogate of the widely employed nucleophilic catalyst dimethylaminopyridine11, and its use will create opportunities to design and engineer enzymes for a wealth of valuable chemical transformations.

Microwave-assisted oxidation of alcohols by hydrogen peroxide catalysed by tetrabutylammonium decatungstate

Galica, Mateusz,Kasprzyk, Wiktor,Bednarz, Szczepan,Bogdal, Dariusz

, p. 1240 - 1244 (2013)

This work deals with catalytic activity of tetrabutylammonium decatungstate(VI) in the oxidation of selected alcohols with hydrogen peroxide as an oxidant using 1,2-dichloroethane/water or acetonitrile/water as a solvent system. Different forms of heating were compared. The highest conversions of substrates were achieved in the two phase system acetonitrile/water using microwave irradiation combined with elevated pressure. Finally, optimum parameters for these reactions in a microwave pressurised reactor were established and discussed.

Resolution of (RS)-phenylglycinonitrile by penicillin acylase-catalyzed acylation in aqueous medium

Chilov, Ghermes G.,Moody, Harold M.,Boesten, Wilhelmus H. J.,Svedas, Vytas K.

, p. 2613 - 2617 (2003)

A new strategy for the biocatalytic resolution of (R,S)-phenylglycinonitrile, a crucial intermediate in the antibiotic industry, has been developed. While former techniques exploit nitrilases or combinations of nitrile hydratases and amidases, manipulating with nitrile functionality, the current approach is based on a highly efficient and enantioselective acylation of the α-amino group with phenylacetic acid catalyzed by a well known enzyme, penicillin acylase from E. coli, in slightly acidic aqueous medium. It is shown that since the condensation product is poorly soluble, removal of (S)-phenylglycinonitrile from the reaction sphere is almost complete and irreversible, favoring kinetics of the process and making high conversion possible. The proposed approach is characterized by high space-time yield and extends the scope of enzymatic synthesis in aqueous medium.

Nickel-Catalyzed Carboxylation of Benzylic C-N Bonds with CO2

Moragas, Toni,Gaydou, Morgane,Martin, Ruben

, p. 5053 - 5057 (2016)

A user-friendly Ni-catalyzed reductive carboxylation of benzylic C-N bonds with CO2 is described. This procedure outperforms state-of-the-art techniques for the carboxylation of benzyl electrophiles by avoiding commonly observed parasitic pathways, such as homodimerization or β-hydride elimination, thus leading to new knowledge in cross-electrophile reactions.

A simple and highly practical oxidation of primary alcohols to acids mediated by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)

Zanka, Atsuhiko

, p. 888 - 889 (2003)

Primary alcohols were quantitatively oxidized in one-pot to acids via 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated oxidation. The reported method is simple and suitable for large scale synthesis.

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Johnson,Jacobs,Schwartz

, p. 1885,1888 (1938)

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Comparison of Spectroscopic and Electrochemical Studies of Disproportionation Equilibria of 1,3,5-Triphenylverdazyl Radical in DMF Containing Carboxylic Acids

Jaworski, Jan S.,Krawczyk, Irena

, p. 43 - 50 (1992)

Stoichiometry and equilibrium constants for the disproportionation of the title radicals in N,N-dimethylformamide containing salicilic, chloroacetic, and phenylacetic acids were determined on the basis of absorption spectra.On the other hand, only apparent equilibrium constants depending on concentrations of an acid and a radical could be obtained from electrochemical measurements at a mercury electrode.Significant differences in reaction stoichiometry and in order of magnitudes of disproportionation constants found under spectroscopic and electrochemical conditionswere discussed in terms of an influence of the electric field in the double layer on the distribution of different associates formed by verdazyl species with acids.Keywords: Disproportionation equilibrium; Effect of the electrode field.

Transformation of Thioacids into Carboxylic Acids via a Visible-Light-Promoted Atomic Substitution Process

Fu, Qiang,Liang, Fu-Shun,Lou, Da-Wei,Pan, Gao-Feng,Wang, Rui,Wu, Min,Xie, Kai-Jun

supporting information, p. 2020 - 2024 (2022/03/31)

A visible-light-promoted atomic substitution reaction for transforming thiocacids into carboxylic acids with dimethyl sulfoxide (DMSO) as the oxygen source has been developed, affording various alkyl and aryl carboxylic acids in over 90% yields. The atomic substitution process proceeds smoothly through the photochemical reactivity of the formed hydrogen-bonding adduct between thioacids and DMSO. A DMSO-involved proton-coupled electron transfer (PCET) and the simultaneous generation of thiyl and hydroxyl radicals are proposed to be key steps for realizing the transformation.

Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate**

Pfennig, Victoria S.,Villella, Romina C.,Nikodemus, Julia,Bolm, Carsten

supporting information, (2022/01/22)

A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.

Polyalkynyl-containing alpha, beta-diamino acid ester derivative compound as well as preparation and application of thereof

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Paragraph 0057-0058, (2021/04/28)

The invention discloses a polyalkynyl-containing alpha, beta-diamino acid ester derivative compound or a pharmaceutically acceptable salt, and an application of the compound or a pharmaceutical composition containing the compound in treating various malignant tumor related diseases such as osteosarcoma, pancreatic cancer, head and neck tumors and the like. The invention further relates to a preparation method of the polyalkynyl-containing alpha, beta-diamino acid ester derivative compound or the pharmaceutically acceptable salt.