- Conversion of oleic acid into azelaic and pelargonic acid by a chemo-enzymatic route
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A chemo-enzymatic approach for the conversion of oleic acid into azelaic and pelargonic acid is herein described. It represents a sustainable alternative to ozonolysis, currently employed at the industrial scale to perform the reaction. Azelaic acid is produced in high chemical purity in 44% isolation yield after three steps, avoiding column chromatography purifications. In the first step, the lipase-mediated generation of peroleic acid in the presence of 35% H2O2 is employed for the self-epoxidation of the unsaturated acid to the corresponding oxirane derivative. This intermediate is submitted to in situ acid-catalyzed opening, to afford 9,10-dihydroxystearic acid, which readily crystallizes from the reaction medium. The chemical oxidation of the diol derivative, using atmospheric oxygen as a stoichiometric oxidant with catalytic quantities of Fe(NO3)3·9·H2O, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and NaCl, affords 9,10-dioxostearic acid which is cleaved by the action of 35% H2O2 in mild conditions, without requiring any catalyst, to give pelargonic and azelaic acid.
- Brenna, Elisabetta,Colombo, Danilo,Di Lecce, Giuseppe,Gatti, Francesco G.,Ghezzi, Maria Chiara,Tentori, Francesca,Tessaro, Davide,Viola, Mariacristina
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- REACTION OF CARBON DIOXIDE WITH A BIMETALLIC OCTADIENYL-BRIDGED PALLADIUM COMPLEX
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Reaction of equimolar amounts of μ-1-3-η:6-8-η-octadienatobis(1,1,1,5,5,5-hexafluoroacetylacetonatopalladium) and triisopropylphosphine gives a bimetalic octadienyl-bridged complex, in which one palladium atom is η1-bound to the terminal carbon of the octadienyl chain.Insertion of CO2 into this Pd-C bond gives a carboxylate complex; acidic decomposition and hydrogenation of the carboxylate complex gives pelargonic acid.The results are discussed in relation to the mechanism of the palladium-catalyzed reaction between butadiene and carbon dioxide.
- Behr, Arno,Ilsemann, Godard von
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- Hydrocarboxylation of terminal alkenes in supercritical carbon dioxide using perfluorinated surfactants
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High selectivity in acids is obtained in the first example of hydrocarboxylation of 1-octene in supercritical carbon dioxide using a Pd/P(4-C6H4-CF3)3 catalyst system and a perfluorinated surfactant. The Royal Society of Chemistry 2006.
- Tortosa-Estorach, Clara,Ruiz, Nuria,Masdeu-Bulto, Anna M.
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- Microwave-induced electrostatic etching: Generation of highly reactive magnesium for application in Grignard reagent formation
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A detailed study regarding the influence of microwave irradiation on the formation of a series of Grignard reagents in terms of rates and selectivities has revealed that these heterogeneous reactions may display a beneficial microwave effect. The interaction between microwaves and magnesium turnings generates violent electrostatic discharges. These discharges on magnesium lead to melting of the magnesium surface, thus generating highly active magnesium particles. As compared to conventional operation the microwave-induced discharges on the magnesium surface lead to considerably shorter initiation times for the insertion of magnesium in selected substrates (i.e. halothiophenes, halopyridines, octyl halides, and halobenzenes). Thermographic imaging and surface characterization by scanning electron microscopy showed that neither selective heating nor a "specific" microwave effect was causing the reduction in initiation times. This novel and straightforward initiation method eliminates the use of toxic and environmentally adverse initiators. Thus, this initiation method limits the formation of by-products. We clearly demonstrated that microwave irradiation enables fast Grignard reagent formation. Therefore, microwave technology is promising for process intensification of Grignard based coupling reactions.
- Van De Kruijs, Bastiaan H. P.,Dressen, Mark H. C. L.,Meuldijk, Jan,Vekemans, Jef A. J. M.,Hulshof, Lumbertus A.
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- Long-chain alkanoic acid esters of lupeol from Dorstenia harmsiana Engl. (Moraceae)
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In addition to lupeol (1a), three long-chain alkanoic acid esters of lupeol, in which two were new, were isolated from the hexane and ethyl acetate twigs extract of Dorstenia harmsiana Engl. (Moraceae). The structures of the new compounds were elucidated
- Poumale, Herve Martial P.,Awoussong, Kenzo Patrice,Randrianasolo, Rivoarison,Simo, Christophe Colombe F.,Ngadjui, Bonaventure Tchaleu,Shiono, Yoshihito
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- Scalable, sustainable and catalyst-free continuous flow ozonolysis of fatty acids
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A simple and efficient catalyst-free protocol for continuous flow synthesis of azelaic acid is developed from the renewable feedstock oleic acid. An ozone and oxygen mixture was used as the reagent for oxidative cleavage of double bond without using any metal catalyst or terminal oxidant. The target product was scaled up to more than 100 g with 86% yield in a white powder form. Complete recycling and reuse of the solvent were established making it a green method. The approach is significantly energy efficient and also has a very small chemical footprint. The methodology has been successfully tested with four fatty acids making it a versatile platform that gives value addition from renewable resources.
- Atapalkar, Ranjit S.,Athawale, Paresh R.,Srinivasa Reddy,Kulkarni, Amol A.
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- Reactive Species and Reaction Pathways for the Oxidative Cleavage of 4-Octene and Oleic Acid with H2O2over Tungsten Oxide Catalysts
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Oxidative cleavage of carbon-carbon double bonds (C-C) in alkenes and fatty acids produces aldehydes and acids valued as chemical intermediates. Solid tungsten oxide catalysts are low cost, nontoxic, and selective for the oxidative cleavage of C-C bonds with hydrogen peroxide (H2O2) and are, therefore, a promising option for continuous processes. Despite the relevance of these materials, the elementary steps involved and their sensitivity to the form of W sites present on surfaces have not been described. Here, we combine in situ spectroscopy and rate measurements to identify significant steps in the reaction and the reactive species present on the catalysts and examine differences between the kinetics of this reaction on isolated W atoms grafted to alumina and on those exposed on crystalline WO3 nanoparticles. Raman spectroscopy shows that W-peroxo complexes (W-(η2-O2)) formed from H2O2 react with alkenes in a kinetically relevant step to produce epoxides, which undergo hydrolysis at protic surface sites. Subsequently, the CH3CN solvent deprotonates diols to form alpha-hydroxy ketones that react to form aldehydes and water following nucleophilic attack of H2O2. Turnover rates for oxidative cleavage, determined by in situ site titrations, on WOx-Al2O3 are 75% greater than those on WO3 at standard conditions. These differences reflect the activation enthalpies (ΔH?) for the oxidative cleavage of 4-octene that are much lower than those for the isolated WOx sites (36 ± 3 and 60 ± 6 kJ·mol-1 for WOx-Al2O3 and WO3, respectively) and correlate strongly with the difference between the enthalpies of adsorption for epoxyoctane (ΔHads,epox), which resembles the transition state for epoxidation. The WOx-Al2O3 catalysts mediate oxidative cleavage of oleic acid with H2O2 following a mechanism comparable to that for the oxidative cleavage of 4-octene. The WO3 materials, however, form only the epoxide and do not cleave the C-C bond or produce aldehydes and acids. These differences reflect the distinct site requirements for these reaction pathways and indicate that acid sites required for diol formation are strongly inhibited by oleic acids and epoxides on WO3 whereas the Al2O3 support provides sites competent for this reaction and increase the yield of the oxidative cleavage products.
- Yun, Danim,Ayla, E. Zeynep,Bregante, Daniel T.,Flaherty, David W.
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- The OsO4-mediated oxidative cleavage of olefins catalyzed by alternative osmium sources
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The OsO4-mediated oxidative cleavage of olefins is compatible with alternative, easier-to-handle osmium sources. Four different osmium sources were employed with favorable results.
- Whitehead, Daniel C.,Travis, Benjamin R.,Borhan, Babak
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- Aliphatic organolithiums by fluorine-lithium exchange: n-octyllithium
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The reaction of 1-fluorooctane (1) with an excess of lithium powder (4-10 equiv.) and DTBB (2-4 equiv.) in THP at 0°C for 5 min gives a solution of the corresponding 1-octyllithium (2), which reacts then with different electrophiles at 0°C (D2O, MeSiCl, ButCHO, Et2CO), or -78°C [ClCO2Me, (PhCH2S)2] or -40°C (CO2) to room temperature to give, after hydrolysis, the expected products (3). The same process applied to 2-fluorooctane gives mainly octane as reaction product, independently on the electrophile used, resulting from a proton abstraction by 2-lithiooctane formed from the reaction medium before addition of the electrophilic reagent.
- Yus, Miguel,Herrera, Raquel P.,Guijarro, Albert
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- Sustainable Process for Production of Azelaic Acid Through Oxidative Cleavage of Oleic Acid
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This work describes two sustainable methods for production and purification of azelaic acid (AA) to replace the current process of ozonolysis of oleic acid (OA). The first proceeds in two steps, coupling smooth oxidation of OA to 9,10-dihydroxystearic acid (DSA) with subsequent oxidative cleavage by sodium hypochlorite. An alternative methodology is also proposed, using a chemocatalytic system consisting of H2O2/H2WO4 for direct oxidative cleavage of the double bond of OA at 373 K. A convenient technique for separation and purification of azelaic acid is also proposed.
- Benessere, Vincenzo,Cucciolito, Maria E.,De Santis, Augusta,Di Serio, Martino,Esposito, Roberto,Ruffo, Francesco,Turco, Rosa
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- Ozonolysis in flow using capillary reactors
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Reactions of n-decene with ozone and subsequent quenching of the formed ozonides were carried out under flow conditions using the standard Vapourtec flow system equipped with a cooled flow cell. The reactions were performed continuously and in the annular flow regime within the circular cross-section channels. Typical flow rates were 0.25-1 mL min-1 for liquid and 25-100 mL min-1 for gas, reactor volumes were 0.07-10 mL formed of 1 mm ID PFA tubing. The reaction temperature was -10 °C. The flow was not always smooth, while waves in the liquid film and droplets in the gas core were observed. Liquid residence times were found to be independent of gas flow rates and increasing with decreasing liquid flow rates. Substrate residence times in the ozonolysis reactor ranged between 1 and 80 s, and complete conversion could be achieved at ～1 s residence time. Two common reductants, triethylphosphite and triphenylphosphine, were examined as to their suitability under flow conditions. Triphenylphosphine achieved faster reduction of the intermediate ozonides, resulting in a greater than 10:1 selectivity for the aldehyde over the corresponding acid. The cooling system provided a safe and efficient control of the highly exothermic reaction system. The configuration of the system allowed the production of chemically significant amounts (1.8 g h-1 at 1.3 ozone equivalents), with minimal amounts of ozonides present at any time.
- Roydhouse, M. D.,Motherwell, W. B.,Ghaini, A.,Constantinou, A.,Cantu-Perez, A.,Gavriilidis, A.
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- New environmentally friendly oxidative scission of oleic acid into azelaic acid and pelargonic acid
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Oleic acid (OA) is a renewable monounsaturated fatty acid obtained from high oleic sunflower oil. This work was focused on the oxidative scission of OA, which yields a mono-acid (pelargonic acid, PA) and a di-acid (azelaic acid, AA) through an emulsifying system. The conventional method for producing AA and PA consists of the ozonolysis of oleic acid, a process which presents numerous drawbacks. Therefore, we proposed to study a new alternative process using a green oxidant and a solvent-free system. OA was oxidized in a batch reactor with a biphasic organic-aqueous system consisting of hydrogen peroxide (H 2O2, 30 %) as an oxidant and a peroxo-tungsten complex Q3{PO4[WO(O2)2]4} as a phase-transfer catalyst/co-oxidant. Several phase-transfer catalysts were prepared in situ from tungstophosphoric acid, H2O2 and different quaternary ammonium salts (Q+, Cl-). The catalyst [C5H5N(n-C16H33)] 3{PO4[WO(O2)2]4} was found to give the best results and was chosen for the optimization of the other parameters of the process. This optimization led to a complete conversion of OA into AA and PA with high yields (>80 %) using the system OA/H 2O2/[C5H5N(n-C16H 33)]3{PO4[WO(O2)2] 4} (1/5/0.02 molar ratio) at 85 C for 5 h. In addition, a new treatment was developed in order to recover the catalyst.
- Godard, Anais,De Caro, Pascale,Thiebaud-Roux, Sophie,Vedrenne, Emeline,Mouloungui, Zephirin
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- Identification and Quantitation of Four New 2-Alkylthiazolidine-4-carboxylic Acids Formed in Orange Juice by a Reaction of Saturated Aldehydes with Cysteine
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Despite several technological efforts to maximize the quality and shelf life of chilled stored not-from-concentrate orange juice, changes in the overall aroma profile might occur during storage. Besides the degradation of terpenoids, a loss of the aroma-active aldehydes, hexanal, octanal, nonanal, and decanal as well-as of 1-penten-3-one were recently confirmed as a major cause for the changes in the aroma profile of orange juice even during storage under aseptic conditions at 0 °C. To unravel the fate of the aroma-active aldehydes, model experiments were carried out considering the oxidation into the corresponding acids as well as a reaction with free amino acids present in orange juice. The oxidation into the acids could be confirmed by isotope labeling experiments; additionally, the reaction of the four aldehydes mentioned above with l-cysteine yielded four new compounds identified as 2-alkylsubstituted thiazolidine-4-carboxylic acids. Their quantitation in orange juice samples by newly developed stable isotope dilution assays revealed that these acids were already present in the fresh samples but were considerably increased after storage. Labeling experiments in orange juice administered with either labeled octanal or labeled cysteine confirmed that the reaction quickly occurs in the juice. The data contribute another puzzle piece to the loss of aroma-active aldehydes during orange juice storage, which may also be relevant in other foods.
- Mall, Veronika,Sellami, Ines,Schieberle, Peter
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- Engineering the nucleotide coenzyme specificity and sulfhydryl redox sensitivity of two stress-responsive aldehyde dehydrogenase isoenzymes of Arabidopsis thaliana
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Lipid peroxidation is one of the consequences of environmental stress in plants and leads to the accumulation of highly toxic, reactive aldehydes. One of the processes to detoxify these aldehydes is their oxidation into carboxylic acids catalyzed by NAD(P)+-dependent ALDHs (aldehyde dehydrogenases). We investigated kinetic parameters of two Arabidopsis thaliana family 3 ALDHs, the cytosolic ALDH3H1 and the chloroplastic isoform ALDH3I1. Both enzymes had similar substrate specificity and oxidized saturated aliphatic aldehydes. Catalytic efficiencies improved with the increase of carbon chain length. Both enzymes were also able to oxidize α,β-unsaturated aldehydes, but not aromatic aldehydes. Activity of ALDH3H1 was NAD+-dependent, whereas ALDH3I1 was able to use NAD+ and NADP+. An unusual isoleucine residue within the coenzyme-binding cleft was responsible for the NAD +-dependence of ALDH3H1. Engineering the coenzyme-binding environment of ALDH3I1 elucidated the influence of the surrounding amino acids. Enzyme activities of both ALDHs were redox-sensitive. Inhibitionwas correlatedwith oxidation of both catalytic and noncatalytic cysteine residues in addition to homodimer formation. Dimerization and inactivation could be reversed by reducing agents. Mutant analysis showed that cysteine residues mediating homodimerization are located in the N-terminal region. Modelling of the protein structures revealed that the redox-sensitive cysteine residues are located at the surfaces of the subunits. The Authors Journal compilation
- Stiti, Naim,Adewale, Isaac O.,Petersen, Jan,Bartels, Dorothea,Kirch, Hans-Hubert
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- Supercritical-fluid-assisted oxidation of oleic acid with ozone and potassium permanganate
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The goal of this research was to determine if any advantages could be realized by conducting the oxidation of oleic acid with ozone and potassium permanganate in supercritical carbon dioxide (SC-CO2). The ozonolysis of oleic acid without SC-CO
- Sparks, Darrell L.,Antonio Estevez,Hernandez, Rafael
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- Liquid-phase catalytic oxidation of unsaturated fatty acids
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Liquid-phase catalytic oxidation of oleic acid with hydrogen peroxide in the presence of various transition metal/metal oxide catalysts was studied in a batch autoclave reactor. Azelaic and pelargonic acids are the major reaction products. Tungsten and tantalum and their oxides in supported and unsupported forms were used as catalysts. Alumina pellets and Kieselguhr powder were used as supports for the catalysts. Tungsten, tantalum, molybdenum, zirconium, and niobium were also examined as catalysts. Tertiary butanol was used as solvent. Experimental results concluded that tungsten and tungstic oxide are more suitable catalysts in terms of their activity and selectivity. The rate of reaction observed in the case of supported catalysts appears to be comparable or superior to that of unsupported catalysts. In pure form, tungsten, tantalum, and molybdenum showed strong catalytic activity in the oxidation reaction; however, except for tantalum the other two were determined to be economically unfeasible. Zirconium and niobium showed very little catalytic activity. Based on the experimental observations, tungstic oxide supported on silica is the most suitable catalyst for the oxidation of oleic acid with 85% of the starting oleic acid converted to the oxidation products in 60 min of reaction with high selectivity for azelaic acid.
- Noureddini,Kanabur
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- Sodium stannate promoted double bond cleavage of oleic acid by hydrogen peroxide over a heterogeneous WO3 catalyst
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The production of valuable mono- and dicarboxylic acids from abundant and renewable vegetable oil sources is of great industrial interest. It is demonstrated by a simple and eco-friendly heterogeneous catalytic system for direct oleic acid (OA) cleavage by hydrogen peroxide to produce azelaic acid (AA) and nonanoic acid (NA). Commercially available tungsten oxide was used as a heterogeneous catalyst without any modification or pretreatment, and sodium stannate was used as a H2O2 stabilizer to improve the efficiency of the oxidant. The sodium stannate additive notably improved the product yields and it could be recycled together with the tungsten oxide catalyst. Isolated product yields up to 89% for azelaic acid and 65% for nonanoic acid were achieved from oleic acid in this simple system, which should be among the best results for oleic acid cleavage in heterogeneous systems. This strategy is also applicable for other catalytic systems for the cleavage of OA or its derivatives. This work provides a potential method for the large scale upgrading of oleic acid.
- Li, Xiukai,Choo Ping Syong, Joel,Zhang, Yugen
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- Product recovery from ionic liquids by solvent-resistant nanofiltration: Application to ozonation of acetals and methyl oleate
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In this work we tackle the problematic separation of reaction products from ionic liquid media. Solvent-resistant nanofiltration proves to be an attractive technique for the separation of non-volatile polar products from ionic liquids. In view of the high compatibility between ozone and ionic liquids, two ozone-mediated model reactions were chosen: firstly the oxidation of acetals to esters in the presence of ozone and secondly the ozonation of methyl oleate to monomethyl azelate and pelargonic acid. The objective was to retain the ionic liquid phase by means of a solvent-resistant nanofiltration membrane, while the organic reaction products permeate through the polymeric membrane. First, the ozonations were studied in order to know the characteristic product compositions. Next, a screening of membranes was performed on synthetic product mixtures. The second generation polyimide-based DuraMem membranes showed the highest rejection, up to 96%, for the evaluated ionic liquids. These DuraMem membranes also proved suitable for the separation of the products on real reaction mixtures, even in a single filtration step.
- Van Doorslaer, Charlie,Glas, Daan,Peeters, Annelies,Cano Odena, Angels,Vankelecom, Ivo,Binnemans, Koen,Mertens, Pascal,De Vos, Dirk
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- Novel route to carboxylic acids via the DCME reaction
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Brown's DCME reaction was successfully performed employing B-alkyl-9-oxa-10-borabicyclo[3.3.2]decanes (1) to provide carboxylic acids (2) in good to excellent yields with complete retention of configuration.
- Soderquist, John A.,Martinez, Judith,Oyola, Yatsandra,Kock, Iveliz
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- Sustainable Oxidative Cleavage of Vegetable Oils into Diacids by Organo-Modified Molybdenum Oxide Heterogeneous Catalysts
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Abstract: Exploiting vegetable oils to produce industrially valuable diacids via an eco-friendly process requires an efficient and recyclable catalyst. In this work, a novel catalytic system based on organo-modified molybdenum trioxide was synthesized by a green hydrothermal method in one simple step, using Mo powder as precursor, hydrogen peroxide, and amphiphilic surfactants cetyltrimethylammonium bromide (CTAB) and tetramethylammonium bromide (TMAB) as capping agents. The synthesized materials were first characterized by different techniques including XRD, SEM, TGA, and FT-IR. Interestingly, various morphologies were obtained depending on the nature of the surfactants and synthetic conditions. The synthesized catalysts were employed in oxidative cleavage of oleic acid, the most abundant unsaturated fatty acid, to produce azelaic and pelargonic acids with a benign oxidant, H2O2. Excellent catalytic activities resulting in full conversion of initial oleic acid were obtained, particularly for CTAB-capped molybdenum oxide (CTAB/Mo molar ratio of 1:3) that gave 83 and 68% yields of production of azelaic and pelargonic acids, respectively. These are the highest yields that have been obtained for this reaction by heterogeneous catalysts up to now. Moreover, the CTAB-capped catalyst could be conveniently separated from the reaction mixture by simple centrifugation and reused without significant loss of activity up to at least four cycles. Graphical Abstract: [Figure not available: see fulltext.].
- Ello, Aimé Serge,Enferadi-kerenkan, Amir,Trokourey, Albert,Do, Trong-On
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- Novel regioselective hydrogenation of alkadienoic acids caused by the addition of water
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The regioselective hydrogenation of 3,8-nonadienoic acid to 8-nonenoic acid was realized by the addition of water with RhCl[P(p-tolyl)3]3 in benzene at 1 atm hydrogen, whereas in the absence of water the reaction mostly gave 3-nonenoic acid. The novel selectivity is caused by both an accelerating effect of water on the hydrogenation of the 3-position and a retarding effect on that of the 8-position.
- Okano, Temon,Kaji, Mitsunari,Isotani, Satoru,Kiji, Jitsuo
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- Synthesis and olfactory properties of new macrolides from unsaturated fatty acids and 1,ω-diols
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A sequence to oxo lactones 1 via Barbier-type Gilman-Van-Ess reaction, sonochemical Lemieux oxidation, one-step ether cleavage iodination and phase transfer catalyzed cyclization is presented. Conversion of the oxo lactones 1 into methyl(en)ated macrolides 11 - 13 resulted in highly potent musk fragrances.
- Rodefeld, Lars,Heinemann, Ines,Tochtermann, Werner
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- Products and mechanisms of ozone reactions with oleic acid for aerosol particles having core-shell morphologies
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Heterogeneous reactions of oleic acid aerosol particles with ozone are studied below 1% relative humidity. The particles have inert polystyrene latex cores (101-nm diameter) coated by oleic acid layers of 2 to 30 nm. The chemical content of the organic layer is monitored with increasing ozone exposure by using an aerosol mass spectrometer. The carbon-normalized percent yields of particle-phase reaction products are 20-35% 9-oxononanoic acid, 1-3% azelaic acid, 1-3% nonanoic acid, and 35-50% other organic molecules (designated as CHOT). There is approximately 25% evaporation, presumably as 1-nonanal. To explain the formation of CHOT molecules and the low yields of azelaic and nonanoic acids, we suggest a chemical mechanism in which the Criegee biradical precursors to azelaic acid and nonanoic acid are scavenged by oleic acid to form CHOT molecules. These chemical reactions increase the carbon-normalized oxygen content (z/x) of the CxH yOz layer from 0.1 for unreacted oleic acid to 0.25 after high ozone exposure. Under the assumption that oxygen content is a predictor of hygroscopicity, our results suggest an increased cloud condensation nuclei activity of atmospherically aged organic particles that initially have alkene functionalities.
- Katrib, Yasmine,Martin, Scot T.,Hung, Hui-Ming,Rudich, Yinon,Zhang, Haizheng,Slowik, Jay G.,Davidovits, Paul,Jayne, John T.,Worsnop, Douglas R.
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- A study into the self-cleaning surface properties - The photocatalytic decomposition of oleic acid
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Thin films of TiO2 exhibiting developed mesoporosity with large surface area and pores ca 10 nm in size were shown efficient photocatalyst in the decomposition of thin layers of oleic acid deposited on their surface. The pore walls of these films were composed of small anatase nanocrystals (ca 40-60%) and some amorphous phase. As major intermediates of the oleic acid decomposition, nonanal and 9-oxononanoic acid were identified. Azelaic and nonanoic acid were detected as well, representing minor intermediates. These compounds have been shown to correspond with the products of a simulated oxidative degradation of cis-3-hexenoic acid computed by means of quantum chemistry. Cis-3-hexenoic acid was chosen as a simplified model of oleic acid having similar but reduced structure. It enabled to perform the theoretical study with a reasonable consumption of computation time. The simulated oxidative degradation of cis-3-hexenoic acid was induced by an attack of hydroxyl radical on the CC double bond. The main reaction pathway led to propanal, 3-oxopropanoic acid, and also hydroxyl radical. The organic products are analogous to the main degradation intermediates of oleic acid, nonanal and 9-oxononanoic acid. The prediction of hydroxyl radical elimination in the final step of the major reaction sequence would mean that it may act as a catalyst causing accelerated degradation of unsaturated compound including fatty acids.
- Rathousky, Ji?í,Kalousek, Vít,Kolá?, Michal,Jirkovsky, Jaromír,Barták, Petr
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- Oxidative carbon-carbon bond cleavage of 1,2-diols to carboxylic acids/ketones by an inorganic-ligand supported iron catalyst
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The carbon-carbon bond cleavage of 1,2-diols is an important chemical transformation. Although traditional stoichiometric and catalytic oxidation methods have been widely used for this transformation, an efficient and valuable method should be further explored from the views of reusable catalysts, less waste, and convenient procedures. Herein an inorganic-ligand supported iron catalyst (NH4)3[FeMo6O18(OH)6]·7H2O was described as a heterogeneous molecular catalyst in acetic acid for this transformation in which hydrogen peroxide was used as the terminal oxidant. Under the optimized reaction conditions, carbon-carbon bond cleavage of 1,2-diols could be achieved in almost all cases and carboxylic acids or ketones could be afforded with a high conversion rate and high selectivity. Furthermore, the catalytic system was used efficiently to degrade renewable biomass oleic acid. Mechanistic insights based on the observation of the possible intermediates and control experiments are presented.
- Chen, Weiming,Xie, Xin,Zhang, Jian,Qu, Jian,Luo, Can,Lai, Yaozhu,Jiang, Feng,Yu, Han,Wei, Yongge
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supporting information
p. 9140 - 9146
(2021/11/23)
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- An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins
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A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh1/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CH3I led to high activity and superb stability.
- Yuan, Qiao,Song, Xiangen,Feng, Siquan,Jiang, Miao,Yan, Li,Li, Jingwei,Ding, Yunjie
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supporting information
p. 472 - 475
(2021/01/25)
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- Biobased Aldehydes from Fatty Epoxides through Thermal Cleavage of β-Hydroxy Hydroperoxides**
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The ring-opening of epoxidized methyl oleate by aqueous H2O2 has been studied using tungsten and molybdenum catalysts to form the corresponding fatty β-hydroxy hydroperoxides. It was found that tungstic acid and phosphotungstic acid gave the highest selectivities (92–93 %) towards the formation of the desired products, thus limiting the formation of the corresponding fatty 1,2-diols. The optimized conditions were applied to a range of fatty epoxides to give the corresponding fatty β-hydroxy hydroperoxides with 30–80 % isolated yields (8 examples). These species were fully characterized by 1H and 13C NMR spectroscopy and HPLC-HRMS, and their stability was studied by differential scanning calorimetry. The thermal cleavage of the β-hydroxy hydroperoxide derived from methyl oleate was studied both in batch and flow conditions. It was found that the thermal cleavage in flow conditions gave the highest selectivity towards the formation of aldehydes with limited amounts of byproducts. The aldehydes were both formed with 68 % GC yield, and nonanal and methyl 9-oxononanoate were isolated with 57 and 55 % yield, respectively. Advantageously, the overall process does not require large excess of H2O2 and only generates water as a byproduct.
- De Dios Miguel, Thomas,Duc Vu, Nam,Lemaire, Marc,Duguet, Nicolas
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p. 379 - 386
(2020/11/30)
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- Ruthenium-catalysed hydroxycarbonylation of olefins
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State-of-the-art catalyst systems for hydroxy- and alkoxycarbonylations of olefins make use of palladium complexes. In this work, we report a complementary ruthenium-catalysed hydroxycarbonylation of olefins applying an inexpensive Ru-precursor (Ru3(CO)12) and PCy3as a ligand. Crucial for the success of this transformation is the use of hexafluoroisopropanol (HFIP) as the solvent in the presence of an acid co-catalyst (PTSA). Overall, moderate to good yields are obtained using aliphatic olefins including the industrially relevant substrate di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various carboxylic acids from unfunctionalized olefins.
- Dühren, Ricarda,Kucmierczyk, Peter,Jackstell, Ralf,Franke, Robert,Beller, Matthias
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p. 2026 - 2030
(2021/04/09)
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- METHOD FOR MANUFACTURING PELARGONIC ACID AND AZELAIC ACID
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The present invention relates to a method for producing pelargonic acid and azelaic acid, and more specifically, provides a method for producing pelargonic acid and azelaic acid, which comprises the following steps of: a) reacting an unsaturated carboxylic acid compound under a tungstic acid catalyst to obtain an intermediate product comprising vicinal diol; and b) reacting the intermediate product under a transition metal hydroxide catalyst to obtain the pelargonic acid and azelaic acid. The production method is capable of producing the pelargonic acid and azelaic acid in a high yield from the unsaturated carboxylic acid compound.
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Paragraph 0055-0083
(2021/07/27)
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- A direct synthesis of carboxylic acidsviaplatinum-catalysed hydroxycarbonylation of olefins
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The platinum-catalysed hydroxycarbonylation of olefins is reported for the first time. Using a combination of PtCl2/2,2′-bis(tert-butyl(pyridin-2-yl)phosphanyl)-1,1′-binaphthalene (Neolephos) in the presence of sulfuric acid [0.6 M] in acetic acid selective carbonylation of terminal aliphatic olefins proceeds to good yields and selectivities to the corresponding carboxylic acids. Comparing the reactivity of different butenes (iso- andn-butenes), the terminal olefin can be selectively carbonylated.
- Schneider, Carolin,Franke, Robert,Jackstell, Ralf,Beller, Matthias
-
p. 2703 - 2707
(2021/05/05)
-
- Ozone-Mediated Amine Oxidation and Beyond: A Solvent-Free, Flow-Chemistry Approach
-
Ozone is a powerful oxidant, most commonly used for oxidation of alkenes to carbonyls. The synthetic utility of other ozone-mediated reactions is hindered by its high reactivity and propensity to overoxidize organic molecules, including most solvents. This challenge can largely be mitigated by adsorbing both substrate and ozone onto silica gel, providing a solvent-free oxidation method. In this manuscript, a flow-based packed bed reactor approach is described that provides exceptional control of reaction temperature and time to achieve improved control and chemoselectivity over this challenging transformation. A powerful method to oxidize primary amines into nitroalkanes is achieved. Examples of pyridine, C-H bond, and arene oxidations are also demonstrated, confirming the system is generalizable to diverse ozone-mediated processes.
- Skrotzki, Eric A.,Vandavasi, Jaya Kishore,Newman, Stephen G.
-
p. 14169 - 14176
(2021/06/30)
-
- Ruthenium-catalysed domino hydroformylation-hydrogenation-esterification of olefins
-
A novel catalytic domino reductive hydroformylation-esterification of olefins is reported. The optimal protocol makes use of an inexpensive Ru carbonyl catalyst and uses acetic acid as both solvent and reactant. In general, moderate to good yields are obtained using aliphatic or aromatic olefins including industrially relevant di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various acetate esters from unfunctionalized olefins.
- Beller, Matthias,Dühren, Ricarda,Franke, Robert,Jackstell, Ralf,Kucmierczyk, Peter,Schneider, Carolin
-
p. 5777 - 5780
(2021/09/10)
-
- Direct oxidative carboxylation of terminal olefins to cyclic carbonates by tungstate assisted-tandem catalysis
-
Tungstate catalysts are well established for olefin epoxidation reactions, while their catalytic activity for CO2 insertion in epoxides is a more recent discovery. This dual reactivity of tungstate prompted the present development of a catalytic tandem process for the direct conversion of olefins into the corresponding cyclic organic carbonates (COCs). Each of the two steps was studied in the presence of the ammonium tungstate ionic liquid catalyst-[N8,8,8,1]2[WO4]-obtained via a benign procedure starting from ammonium methylcarbonate ionic liquids. The catalytic epoxidation first step was optimised on 1-decene as model substrate, using H2O2 as benign oxidant, [N8,8,8,1]2[WO4] as catalyst and phosphoric acid as promoter affording quantitative conversion with 92% selectivity towards decene oxide. Unfortunately, the addition of CO2 from the start (auto-tandem catalysis) gave low yields of decene carbonate (10%). On the contrary, the addition of 1 atm CO2 and tetrabutyl ammonium iodide after completion of the epoxidation first step without any intermediate work-up (assisted-tandem catalysis) afforded a 94% yield in decene carbonate. The protocol could be scaled up to a 10 gram scale. The scope of the reaction was demonstrated for primary aliphatic olefins with different alkyl chain lengths (C6-C16), while cyclic and aromatic activated olefins such as cyclohexene and styrene suffered from the formation of undesired overoxidation products in the first step.
- Calmanti, Roberto,Perosa, Alvise,Selva, Maurizio
-
p. 7609 - 7619
(2021/10/12)
-
- Reactions between lithiated 1,3-dithiane oxides and trialkylboranes
-
Various 2-substituted-1,3-dithiane oxides (1-oxide and 1,3-dioxide) have been metalated and reacted for the first time with a trialkylborane (trioctylborane). The 2-chloro-1,3-dioxide results in migration of an octyl group from boron to carbon with the displacement of chloride and gives nonanoic acid after oxidation, but there is no evidence for a second migration involving displacement of a sulfenate group. The reaction involving lithiation of the 2-methoxy-1-oxide results in two migrations, with the displacement of both the methoxy group and the thiolate unit of the dithiane ring, giving dioctyl ketone after oxidation, but the yield is low, primarily because thiophilic addition of the lithiating agent predominates over lithiation. Again, there is no evidence for the displacement of the sulfenate unit. However, the intermediate prior to oxidation can be treated with trifluoroacetic anhydride to induce a Pummerer rearrangement, and the presumed trifluoroacetoxyalkylthiolate group then acts as a novel leaving group and is displaced, resulting in trioctylmethanol on oxidation, but the yield is again very low.
- El-Hiti, Gamal A.,Elliott, Mark C.,Saleh, Basil A.,Smith, Keith
-
p. 591 - 603
(2021/09/22)
-
- METAL-FREE METHOD FOR OXIDATIVE CLEAVAGE OF VIC-DIOLS TO CARBOXYLIC ACIDS
-
The invention relates to a simple and efficient metal-free method for oxidative cleavage of vic-diols, in particular those derived from fatty esters, to the corresponding carboxylic acids, using a cheap, safe and environmentally friendly oxidant under mild conditions wherein oxone? is used as an oxidant and a halide as a catalyst in presence of the accurate organic solvent.
- -
-
Page/Page column 8; 9
(2021/11/13)
-
- Oxidation of aromatic and aliphatic aldehydes to carboxylic acids by Geotrichum candidum aldehyde dehydrogenase
-
Oxidation reaction is one of the most important and indispensable organic reactions, so that green and sustainable catalysts for oxidation are necessary to be developed. Herein, biocatalytic oxidation of aldehydes was investigated, resulted in the synthesis of both aromatic and aliphatic carboxylic acids using a Geotrichum candidum aldehyde dehydrogenase (GcALDH). Moreover, selective oxidation of dialdehydes to aldehydic acids by GcALDH was also successful.
- Hoshino, Tomoyasu,Yamabe, Emi,Hawari, Muhammad Arisyi,Tamura, Mayumi,Kanamaru, Shuji,Yoshida, Keisuke,Koesoema, Afifa Ayu,Matsuda, Tomoko
-
-
- The plant pathogen enzyme AldC is a long-chain aliphatic aldehyde dehydrogenase
-
Aldehyde dehydrogenases are versatile enzymes that serve a range of biochemical functions. Although traditionally considered metabolic housekeeping enzymes because of their ability to detoxify reactive aldehydes, like those generated from lipid peroxidation damage, the contributions of these enzymes to other biological processes are widespread. For example, the plant pathogen Pseudomonas syringae strain PtoDC3000 uses an indole-3-acetaldehyde dehydrogenase to synthesize the phytohormone indole-3-acetic acid to elude host responses. Here we investigate the biochemical function of AldC from PtoDC3000. Analysis of the substrate profile of AldC suggests that this enzyme functions as a long-chain aliphatic aldehyde dehydrogenase. The 2.5 ? resolution X-ray crystal of the AldC C291A mutant in a dead-end complex with octanal and NAD1 reveals an apolar binding site primed for aliphatic aldehyde substrate recognition. Functional characterization of site-directed mutants targeting the substrate- and NAD(H)-binding sites identifies key residues in the active site for ligand interactions, including those in the “aromatic box” that define the aldehyde-binding site. Overall, this study provides molecular insight for understanding the evolution of the prokaryotic aldehyde dehydrogenase superfamily and their diversity of function.
- Lee, Soon Goo,Harline, Kate,Abar, Orchid,Akadri, Sakirat O.,Bastian, Alexander G.,Chen, Hui-Yuan S.,Duan, Michael,Focht, Caroline M.,Groziak, Amanda R.,Kao, Jesse,Kottapalli, Jagdeesh S.,Leong, Matthew C.,Lin, Joy J.,Liu, Regina,Luo, Joanna E.,Meyer, Christine M.,Mo, Albert F.,Pahng, Seong Ho,Penna, Vinay,Raciti, Chris D.,Srinath, Abhinav,Sudhakar, Shwetha,Tang, Joseph D.,Cox, Brian R.,Holland, Cynthia K.,Cascella, Barrie,Cruz, Wilhelm,McClerkin, Sheri A.,Kunkel, Barbara N.,Jez, Joseph M.
-
p. 13914 - 13926
(2020/12/09)
-
- Method for preparing carboxylic acid by catalyzing aldehyde oxidation with N-heterocyclic carbene
-
The invention discloses a method for preparing carboxylic acid by catalyzing aldehyde oxidation with N-heterocyclic carbene, and relates to the field of catalytic technology. The method comprises thefollowing steps: taking deionized water as a solvent and aldehyde as a reaction substrate, adding alkali into a reaction system, taking air as an oxidant and N-heterocyclic carbene as a catalyst required by the reaction, and carrying out catalytic oxidation on aldehyde at room temperature to 80 DEG C to generate a corresponding reaction product. The method has the beneficial effects that the N-heterocyclic carbene is used as the catalyst, no organic solvent is needed in the reaction process, the reaction process is green and safe, and the reaction yield is high.
- -
-
Paragraph 0039-0043; 0056-0059; 0126-0128
(2020/11/25)
-
- Two-way homologation of aliphatic aldehydes: Both one-carbon shortening and lengthening via the same intermediate
-
Aliphatic aldehydes can be homologated to both one-carbon shorter and one-carbon longer homologous carbonyl compounds through the 2–4 steps of reactions via the same intermediates, β,γ-unsaturated α-nitrosulfones, prepared from the proline-catalyzed sequential reactions of several aliphatic aldehydes with phenylsulfonylnitromethane. While the oxidative cleavage of the key intermediates gave one-carbon less homologous carbonyl compounds, the reduction of the same key intermediates followed by an oxidation produced one-carbon more homologous carbonyl compounds.
- Yoo, Jae Won,Seo, Youngran,Park, Jong Beom,Kim, Young Gyu
-
-
- Method for catalytically oxidizing primary alcohol into corresponding carboxylic acid and simultaneously co-producing corresponding alpha olefin
-
The invention relates to a method for catalytically oxidizing primary alcohol into corresponding carboxylic acid and simultaneously co-producing corresponding alpha olefin. The method comprises the following steps: mixing primary alcohol shown as a substrate (I), a catalyst cobalt salt, a nitrogen-containing ligand and a solvent, refluxing and stirring for 4-48 hours in an oxygen or air atmospherewith a certain pressure, and distilling and separating the reacted liquid to obtain carboxylic acid shown as (II) and alpha olefin in a certain proportion. The cobalt salt catalyst used in the methodis cheap and easy to obtain, the used nitrogen-containing ligand is a commercial nitrogen-containing compound, the used oxidant is oxygen or air, the reaction condition is mild, and various primary alcohols can be converted into corresponding carboxylic acids and alpha olefins at a high conversion rate under the condition of low cost.
- -
-
Paragraph 0038-0039
(2020/12/30)
-
- Synthesis of Branched Biolubricant Base Oil from Oleic Acid
-
The mature manufacturing of synthetic lubricants (poly-α-olefins, PAO) proceeds through oligomerization, polymerization, and hydrogenation reactions of petrochemical ethylene. In this work, we utilize the inexpensive bio-derived oleic acid as raw material to synthesize a crotch-type C45 biolubricant base oil via a full-carbon chain synthesis without carbon loss. It contains several cascade chemical processes: oxidation of oleic acid to azelaic acid (further esterification to dimethyl azelate) and nonanoic acid (both C9 chains). The latter is then selectively hydrogenated to nonanol and brominated to the bromo-Grignard reagent. In a next step, a C45 biolubricant base oil is formed by nucleophilic addition (NPA) of excessive C9 bromo-Grignard reagent with dimethyl azelate, followed by subsequent hydrodeoxygenation. The specific properties of the prepared biolubricant base oil are almost equivalent to those of the commercial lubricant PAO6 (ExxonMobil). This process provides a new promising route for the production of value-added biolubricant base oils.
- Chen, Shuang,Wu, Tingting,Zhao, Chen
-
p. 5516 - 5522
(2020/09/07)
-
- SYNTHESIS OF HYPERVALENT IODINE REAGENTS WITH DIOXYGEN
-
Methods of synthesis of hypervalent iodine reagents and methods for oxidation of organic compounds are disclosed.
- -
-
Paragraph 0165-0169
(2019/01/15)
-
- Dehydrogenation of Alcohols to Carboxylic Acid Catalyzed by in Situ-Generated Facial Ruthenium- CPP Complex
-
A selective catalytic system for the dehydrogenation of primary alcohols to carboxylic acids using a facial ruthenium complex generated in situ from the [Ru(COD)Cl2]n and a hybrid N-heterocyclic carbene (NHC)-phosphine-phosphine ligand (CPP) has been first reported. The facial coordination model was unveiled by NMR analysis of the reaction mixture. Such a fac-ruthenium catalyst system exhibited high catalytic activity and stability, and a high turnover number of 20 000 could be achieved with catalyst loading as low as 0.002 mol %. The exceedingly high catalyst stability was tentatively attributed to both the anchoring role of NHC and the hemi-lability of phosphines. The catalytic system also features a wide substrate scope. In particular, the facial coordination of CPP ligands was found to be beneficial for sterically hindered alcohols, and ortho-substituted benzylic alcohols and bulky adamantanyl methanol as well as cholesterol were all found to be viable dehydrogenation substrates.
- Liu, Hui-Min,Jian, Lei,Li, Chao,Zhang, Chun-Chun,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua,Li, Rui-Xiang
-
p. 9151 - 9160
(2019/08/12)
-
- Pd-Catalyzed Highly Chemo- And Regioselective Hydrocarboxylation of Terminal Alkyl Olefins with Formic Acid
-
An efficient Pd-catalyzed hydrocarboxylation of alkenes with HCOOH is described. A wide variety of linear carboxylic acids bearing various functional groups can be obtained with excellent chemo- and regioselectivities under mild reaction conditions. The reaction process is operationally simple and requires no handling of toxic CO.
- Ren, Wenlong,Chu, Jianxiao,Sun, Fei,Shi, Yian
-
supporting information
p. 5967 - 5970
(2019/08/26)
-
- PRODUCTION OF CARBOXYLIC ACIDS FROM VICINAL DIOLS
-
The present invention relates to a process of preparation of carboxylic acids by oxidative cleavage of at least one vicinal diol or an epoxide in the presence of an oxidant comprising molecular oxygen and a heterogeneous catalyst comprising a copper oxide.
- -
-
Page/Page column 13; 15; 16
(2019/06/11)
-
- Carbonylative Transformation of Allylarenes with CO Surrogates: Tunable Synthesis of 4-Arylbutanoic Acids, 2-Arylbutanoic Acids, and 4-Arylbutanals
-
In this Communication, procedures for the selective synthesis of 4-arylbutanoic acids, 2-arylbutanoic acids, and 4-arylbutanals from the same allylbenzenes have been developed. With formic acid or TFBen as the CO surrogate, reactions proceed selectively and effectively under carbon monoxide gas-free conditions.
- Wu, Fu-Peng,Li, Da,Peng, Jin-Bao,Wu, Xiao-Feng
-
supporting information
p. 5699 - 5703
(2019/08/01)
-
- Synthetic method of terminal carboxylic acid
-
The invention discloses a synthetic method of a terminal carboxylic acid. The synthetic method is characterized by comprising the steps of adding an olefin represented by a formula (3) shown in the description, formic acid, acetic anhydride, Pd(OAc)2 and a monophosphorus ligand TFPP into an organic solvent in a proportion, carrying out hydrogen carbonylation reaction on the olefin represented by the formula (3) shown in the description, formic acid and acetic anhydride at 80-90 DEG C for 48h-72h under the catalysis of the metal palladium salt Pd(OAc)2 and the monophosphorus ligand TFPP so as to obtain the terminal carboxylic acid represented by a formula shown in the description, and separating a target product, namely the terminal carboxylic acid after the reaction is finished, wherein olefin represented by the formula (3) is selected from cycloolefins, or linear olefins of which the R1 is electron donating groups. By virtue of the method disclosed by the invention, corresponding terminal carboxylic acid and a derivative thereof can be prepared through the reaction under mild conditions of low temperature and no high pressure; and the steps of the synthetic method are simple and convenient, the operation is convenient, the yield is high, the energy source can be greatly saved, and the synthetic efficiency can be greatly improved.
- -
-
Page/Page column 0039-0042
(2019/11/21)
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- Method for preparing nonanoic acid and azelaic acid
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The invention belongs to a synthesis method, particularly a method for preparing nonanoic acid and azelaic acid by using oleic acid. According to the method, oleic acid and glacial acetic acid are subjected to ozone oxidation and oxidative cleavage, the reactants are further extracted and purified to respectively obtain high purity nonanoic acid and high purity azelaic acid, and a mass ratio of oleic acid to glacial acetic acid is 1:2-4. According to the present invention, the azelaic acid purification is performed with near boiling water without the additional catalyst, such that the method has advantages of simple process, low cost and environmental protection, and is suitable for large-scale production.
- -
-
Paragraph 0023-0049
(2019/01/23)
-
- PROCESS FOR THE DIRECT CONVERSION OF ALKENES TO CARBOXYLIC ACIDS
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Process for the direct conversion of alkenes to carboxylic acids.
- -
-
Paragraph 0029-0032
(2019/07/10)
-
- Synthesis of Carboxylic Acids by Palladium-Catalyzed Hydroxycarbonylation
-
The synthesis of carboxylic acids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers, cosmetics, pharmaceuticals, agrochemicals, and other manufactured chemicals. Although hydroxycarbonylations of olefins have been known for more than 60 years, currently known catalyst systems for this transformation do not fulfill industrial requirements, for example, stability. Presented herein for the first time is an aqueous-phase protocol that allows conversion of various olefins, including sterically hindered and demanding tetra-, tri-, and 1,1-disubstituted systems, as well as terminal alkenes, into the corresponding carboxylic acids in excellent yields. The outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key-to-success is the use of a built-in-base ligand under acidic aqueous conditions. This catalytic system is expected to provide a basis for new cost-competitive processes for the industrial production of carboxylic acids.
- Sang, Rui,Kucmierczyk, Peter,Dühren, Ricarda,Razzaq, Rauf,Dong, Kaiwu,Liu, Jie,Franke, Robert,Jackstell, Ralf,Beller, Matthias
-
supporting information
p. 14365 - 14373
(2019/09/06)
-
- USES OF VANADIUM TO OXIDIZE ALDEHYDES AND OZONIDES
-
The present invention relates to uses of vanadium to convert aldehydes and ozonides into their respective acids and/or ketones. More particularly, this invention relates to the oxidative work-ups following ozonolysis using vanadium, using vanadium during ozonolysis, and using vanadium to oxidize aldehydes in general. The invention also relates to methods comprising the ozonolysis of oleyl alcohol in the presence of either an acid or an alcohol.
- -
-
Paragraph 00052
(2018/04/13)
-
- A biocatalytic method for the chemoselective aerobic oxidation of aldehydes to carboxylic acids
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Herein, we present a study on the oxidation of aldehydes to carboxylic acids using three recombinant aldehyde dehydrogenases (ALDHs). The ALDHs were used in purified form with a nicotinamide oxidase (NOx), which recycles the catalytic NAD+ at the expense of dioxygen (air at atmospheric pressure). The reaction was studied also with lyophilised whole cell as well as resting cell biocatalysts for more convenient practical application. The optimised biocatalytic oxidation runs in phosphate buffer at pH 8.5 and at 40 °C. From a set of sixty-one aliphatic, aryl-Aliphatic, benzylic, hetero-Aromatic and bicyclic aldehydes, fifty were converted with elevated yield (up to >99%). The exceptions were a few ortho-substituted benzaldehydes, bicyclic heteroaromatic aldehydes and 2-phenylpropanal. In all cases, the expected carboxylic acid was shown to be the only product (>99% chemoselectivity). Other oxidisable functionalities within the same molecule (e.g. hydroxyl, alkene, and heteroaromatic nitrogen or sulphur atoms) remained untouched. The reaction was scaled for the oxidation of 5-(hydroxymethyl)furfural (2 g), a bio-based starting material, to afford 5-(hydroxymethyl)furoic acid in 61% isolated yield. The new biocatalytic method avoids the use of toxic or unsafe oxidants, strong acids or bases, or undesired solvents. It shows applicability across a wide range of substrates, and retains perfect chemoselectivity. Alternative oxidisable groups were not converted, and other classical side-reactions (e.g. halogenation of unsaturated functionalities, Dakin-Type oxidation) did not occur. In comparison to other established enzymatic methods such as the use of oxidases (where the concomitant oxidation of alcohols and aldehydes is common), ALDHs offer greatly improved selectivity.
- Knaus, Tanja,Tseliou, Vasilis,Humphreys, Luke D.,Scrutton, Nigel S.,Mutti, Francesco G.
-
supporting information
p. 3931 - 3943
(2018/09/11)
-
- Highly efficient oxidative cleavage of alkenes and cyanosilylation of aldehydes catalysed by magnetically recoverable MIL-101
-
The catalytic activity of magnetically recoverable MIL-101 was investigated in the oxidation of alkenes to carboxylic acids and cyanosilylation of aldehydes. MIL-101 was treated with Fe3O4 and the prepared catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, N2 adsorption measurements, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and inductively coupled plasma analysis. The catalytic active sites in this heterogeneous catalyst are Cr3+ nodes of the MIL-101 framework. This heterogeneous catalyst has the advantages of excellent yields, short reaction times and reusability several times without significant decrease in its initial activity and stability in both oxidation and cyanosilylation reactions. Its magnetic property allows its easy separation using an external magnetic field.
- Nourian, Maryam,Zadehahmadi, Farnaz,Kardanpour, Reihaneh,Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
-
-
- Oxidation Catalysis by an Aerobically Generated Dess–Martin Periodinane Analogue
-
Hypervalent iodine(V) reagents, such as Dess–Martin periodinane (DMP) and 2-iodoxybenzoic acid (IBX), are broadly useful oxidants in chemical synthesis. Development of strategies to generate these reagents from dioxygen (O2) would immediately enable use of O2 as a terminal oxidant in a broad array of substrate oxidation reactions. Recently we disclosed the aerobic synthesis of I(III) reagents by intercepting reactive oxidants generated during aldehyde autoxidation. In this work, aerobic oxidation of iodobenzenes is coupled with disproportionation of the initially generated I(III) compounds to generate I(V) reagents. The aerobically generated I(V) reagents exhibit substrate oxidation chemistry analogous to that of DMP. The developed aerobic generation of I(V) has enabled the first application of I(V) intermediates in aerobic oxidation catalysis.
- Maity, Asim,Hyun, Sung-Min,Wortman, Alan K.,Powers, David C.
-
supporting information
p. 7205 - 7209
(2018/05/29)
-
- A Co2B Mediated NaBH4 Reduction Protocol Applicable to a Selection of Functional Groups in Organic Synthesis
-
A high-yielding and high-rate reduction method that operates with alkenes, alkynes, azides, nitriles, and nitroarenes was developed and optimized. The method makes use of sodium borohydride reduction of CoSO4 under release of hydrogen along with the formation of Co2B as a nanoparticle material. The produced Co2B activates the various functional groups for hydride reduction. The protocol was proven to operate with an assortment of functional groups to provide good to excellent yields. Furthermore, the reduction method was successfully adapted, implemented, and developed for a continuous flow approach using the multi-jet oscillating disk (MJOD) flow reactor platform at atmospheric pressure.
- Lundevall, Frida Johanne,Elumalai, Vijayaragavan,Drageset, Audun,Totland, Christian,Bj?rsvik, Hans-René
-
supporting information
p. 3416 - 3425
(2018/07/29)
-
- Broadly Applicable Ytterbium-Catalyzed Esterification, Hydrolysis, and Amidation of Imides
-
An efficient, broadly applicable, operationally simple, and divergent process for the transformation of imides into a range of carboxylic acid derivatives under mild conditions is reported. By simply using catalytic amounts of ytterbium(III) triflate as a Lewis acid promoter in the presence of alcohols, water, amines, or N,O-dimethylhydroxylamine, a broad range of imides is smoothly and readily converted to the corresponding esters, carboxylic acids, amides, and Weinreb amides in good yields. This method notably enables an easy cleavage of oxazolidinone-based auxiliaries.
- Guissart, Céline,Barros, Andre,Rosa Barata, Luis,Evano, Gwilherm
-
p. 5098 - 5102
(2018/09/13)
-
- CATALYTIC CARBOXYLATION OF ACTIVATED ALKANES AND/OR OLEFINS
-
The present invention relates to a method of reacting starting materials with an activating group, namely alkanes carrying a leaving group and/or olefins, with carbon dioxide under transition metal catalysis to give carboxyl group-containing products. It is a special feature of the method of the present invention that the carboxylation predominantly takes place at a preferred position of the molecule irrespective of the position of the activating group. The carboxylation position is either an aliphatic terminus of the molecule or it is a carbon atom adjacent to a carbon carrying an electron withdrawing group. The course of the reaction can be controlled by appropriately choosing the reaction conditions to yield the desired regioisomer.
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Page/Page column 64; 72; 73
(2018/02/28)
-
- Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
-
Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
- Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
-
supporting information
p. 3967 - 3970
(2018/04/23)
-
- Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling
-
A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO2 catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.
- Fan, Yonghui,Li, Shenggang,Bao, Jingxian,Shi, Lei,Yang, Yanzhang,Yu, Fei,Gao, Peng,Wang, Hui,Zhong, Liangshu,Sun, Yuhan
-
supporting information
p. 3450 - 3456
(2018/08/06)
-
- Process for producing long chain amino acids and dibasic acids
-
There is disclosed a process for the production of long chain amino acid and long chain dibasic acid, comprising: (1) reacting long chain keto fatty acid with hydroxylamine or subjecting keto fatty acid to an ammoximation reaction to yield an oxime fatty acid; (2) subjecting the oxime fatty acid to the Beckmann rearrangement to yield a mixture of two amide fatty acids; (3) hydrolyzing the mixed amide fatty acids to produce long chain amino acid, long chain dibasic acid, short chain alkylamine, and alkanoic acid.
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-
Page/Page column 9-10
(2018/09/21)
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- A Two-Step Oxidative Cleavage of 1,2-Diol Fatty Esters into Acids or Nitriles by a Dehydrogenation–Oxidative Cleavage Sequence
-
Dehydrogenative oxidation of vicinal alcohols catalyzed by a commercially 64 wt.% Ni/SiO2 catalyst leads to the formation of α-hydroxyketone. This first step was developed without additional solvent according to two protocols: “under vacuum” or “with an olefin scavenger”. The synthesis of ketols was carried out with good conversions and selectivities. The recyclability of the supported nickel was also studied. Acyloin was then cleaved with oxidative reagent “formic acid/hydrogen peroxide”, which is cheap and can be used on a large scale for industrial oxidation processes. The global yield of this sequential system was up to 80 % to pelargonic acid and azelaic acid monomethyl ester without intermediate purification. By treating the acyloin intermediate with hydroxylamine, nitriles were obtained with a good selectivity.
- Guicheret, Boris,Bertholo, Yann,Blach, Philippe,Raoul, Yann,Métay, Estelle,Lemaire, Marc
-
p. 3431 - 3437
(2018/09/06)
-
- Catalytic oxidation of α-alkenes with hydrogen peroxide to carboxylic acids in the presence of peroxopolyoxotungstate complexes
-
Fine organic synthesis investigation has been performed, focusing on the possibility of efficient oxidation of α-alkenes by hydrogen peroxide under conditions of phase transfer catalysis using bifunctional metal complex catalysts based on peroxotungsten compounds of general formula Q3{PO4[WO(O2)2]4}, where Q is organic cation containing quaternary nitrogen atom. Catalysts screening has been done at oxidation of octene-1, decene-1 and dodecene-1 by 30% aqueous hydrogen peroxide to obtain carboxylic acids: heptanoic, nonanoic and undecanoic acids being of importance since used as precursors in the synthesis of various organic and biologically active compounds. This approach to the synthesis of carboxylic acids may be of interest for the processes of “green chemistry” occurring under mild conditions (Т??100?°С, Р – atm) in one stage without organic solvents, and providing high target product yields (86–97%).
- Pai,Selivanova,Oleneva,Berdnikova,Beskopyl'nyi
-
-
- Amphiphilic dipyridinium-phosphotungstate as an efficient and recyclable catalyst for triphasic fatty ester epoxidation and oxidative cleavage with hydrogen peroxide
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A novel amphiphilic dipyridinium peroxophosphotungstate ion pair was developed as a selective and recyclable catalyst for the triphasic epoxidation of fatty acids and esters with hydrogen peroxide. The synthesis of the catalyst was studied extensively by solid and liquid phase 31P nuclear magnetic resonance (NMR). The oxidation of vegetable oils is of prime importance for the production of lubricants, plasticizers, polymer stabilizers and other olefinic compounds. Based on the oxidizing activity of peroxophosphotungstates, we designed a lipophilic phase transfer agent that renders the active complex insoluble in the reaction media, without having to support it on a matrix. This affords a catalyst combining the activity of homogeneous catalysts and the recyclability of heterogeneous systems. We show that this catalyst is able to fully epoxidize methyl oleate with excellent selectivity, with a turnover frequency of 149 at 60 °C, and can be easily recycled, to reach a record turn over number of 1868. A larger scale experiment on 13 grams and a scope including linoleic and ricinoleic acids were also demonstrated. The catalyst also shows excellent activity and selectivity for the oxidative cleavage of methyl oleate and the oxidation of small olefins.
- De La Garza, Luis Carlos,De Oliveira Vigier, Karine,Chatel, Gregory,Moores, Audrey
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p. 2855 - 2862
(2017/07/24)
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- A Ligand-Directed Catalytic Regioselective Hydrocarboxylation of Aryl Olefins with Pd and Formic Acid
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An effective Pd-catalyzed hydrocarboxylation of aryl olefins with Ac2O and formic acid is described. A variety of 2- and 3-arylpropanoic acids can be regioselectively formed by the judicious choice of ligand without the use of toxic CO gas.
- Liu, Wei,Ren, Wenlong,Li, Jingfu,Shi, Yuan,Chang, Wenju,Shi, Yian
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supporting information
p. 1748 - 1751
(2017/04/11)
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- Site-Selective Catalytic Carboxylation of Unsaturated Hydrocarbons with CO2 and Water
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A catalytic protocol that reliably predicts and controls the site-selective incorporation of CO2 to a wide range of unsaturated hydrocarbons utilizing water as formal hydride source is described. This platform unlocks an opportunity to catalytically repurpose three abundant, orthogonal feedstocks under mild conditions.
- Gaydou, Morgane,Moragas, Toni,Juliá-Hernández, Francisco,Martin, Ruben
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supporting information
p. 12161 - 12164
(2017/09/12)
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- Palladium-Catalyzed Isomerization/(Cyclo)carbonylation of Pentenamides: a Mechanistic Study of the Chemo- and Regioselectivity
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A new isomerizing ring-closing amidocarbonylation reaction is reported using Pd catalysis with bulky diphosphane ligands. From terminal as well as internal pentenamide isomers (PAs), cyclic imides were obtained in good yield (92 %) with cationic Pd catalysts supported by bis-PCg ligands (PCg=6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamant-6-yl). An excess of strong acid is required to obtain high selectivity for imide products. From a low-temperature NMR study it was deduced that N coordination of the amide moiety is responsible for a high selectivity to cyclic imide products. In weakly acidic conditions, O coordination of the amide functionality leads to the formation of cyanoacids (i.e., 5-cyanovaleric acid, 2-methyl-4-cyanobutyric acid and 2-ethyl-3-cyanopropionic acid). It is proposed that the formation of these cyanoacids occurs through a novel intramolecular tandem dehydrating hydroxycarbonylation reaction of PAs. This reaction also occurs in intermolecular versions of amidocarbonylation with mixtures of alkene and amide substrates. Experiments with N-alkylated amides have been instrumental in developing mechanistic models. The strong acid co-catalyst ensures double-bond isomerization to occur faster than product formation, resulting in the same product mixture, irrespective of the use of terminal or internal pentenamides. The remaining challenge is to arrive at the desired adipimide by overcoming the undesirable regioselectivity caused by chelation of the amide.
- Limburg, Bart,Gloaguen, Yann,de Bruijn, Hans M.,Drent, Eite,Bouwman, Elisabeth
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p. 2961 - 2971
(2017/08/15)
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- MIXED OXIDES FOR THE OXIDATIVE CLEAVAGE OF LIPIDS USING OXYGEN TO AFFORD MONO- AND DI-CARBOXYLIC ACIDS
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This invention relates to the synthesis of new catalysts based on earth crust abundant mixed oxides that can produce cleavage of fatty acids (FA), FA methyl esters, or even lipids in a single step using oxygen as oxidant in solventless conditions.
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Page/Page column 13-14
(2017/12/29)
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- Fatty Acid Chain Shortening by a Fungal Peroxygenase
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A recently discovered peroxygenase from the fungus Marasmius rotula (MroUPO) is able to catalyze the progressive one-carbon shortening of medium and long-chain mono- and dicarboxylic acids by itself alone, in the presence of H2O2. The mechanism, analyzed using H218O2, starts with an α-oxidation catalyzed by MroUPO generating an α-hydroxy acid, which is further oxidized by the enzyme to a reactive α-keto intermediate whose decarboxylation yields the one-carbon shorter fatty acid. Compared with the previously characterized peroxygenase of Agrocybe aegerita, a wider heme access channel, enabling fatty acid positioning with the carboxylic end near the heme cofactor (as seen in one of the crystal structures available) could be at the origin of the unique ability of MroUPO shortening carboxylic acid chains.
- Olmedo, Andrés,Río, José C. del,Kiebist, Jan,Ullrich, René,Hofrichter, Martin,Scheibner, Katrin,Martínez, Angel T.,Gutiérrez, Ana
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supporting information
p. 16985 - 16989
(2017/11/27)
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