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International audience; Xylose can be selectively converted to xylitol in water, with an optimized yield of 98%, in the presence of a simple silica supported metallic cobalt-Co/SiO2-catalyst. This catalyst displays initial outstanding catalytic properties in proper solvent, the best one being pure water. Recyclability studies show a moderate deactivation of the catalyst, while selectivity to xylitol remains almost unchanged after 4 cycles, confirming the promising character of this catalyst formulation for the xylitol production process. Xylose is a product issued from the hydrolysis of beechwood hemicelluloses. Different routes exists for the valorisation of xylose, amongst the selective hydrogenation to xylitol (scheme 1). Xylitol is an extensively used molecule in food, cosmetics, and pharmaceutical industry[1-4]. Xylitol has then been identified as one of the top-twelve value added chemicals that can be obtained from biomass [5]. As an example, xylitol is a valuable water soluble sweetener due to its atypical properties amongst, compared to sucrose, a higher sweetness strength and a lower energy capacity. Today, xylitol is widely incorporated in daily consumed products (chewing gums, chocolates, toothpastes, etc.) [6]. With an estimated market of 340 M$, xylitol is becoming the most popular "natural" sweeteners [7]. Industrial production of xylitol by selective catalytic hydrogenation appears as an economically viable approach. Scheme 1. Hydrogenation of xylose to xylitol. Xylitol can be produced by catalytic hydrogenation in the presence of RANEY® nickel. Reaction is performed in liquid phase, under high hydrogen pressure and temperature in batch-type reactors [8]. Selectivity above 90%, at high conversion degree can be obtained at 80-130°C under 40-70 bar of H2 (5 wt.% catalyst of the xylose mass present at 40-60 wt.% in water) in the presence of RANEY® nickel. Despite the high selectivity and activity reached using this catalyst, with economic advantages related to the use of noble metal free catalysts for the reaction, the intrinsic properties of the nickel, amongst toxicity and limited stability,[8-9] makes the research of efficient catalyst substitutes. Indeed, the use of xylitol for food applications imply the absence of any trace of nickel in final product, nickel being recognized as a carcinogen compound. Most of recent studies were devoted to the study of supported noble metals, such as Ru, Rh and Pd, in monometallic or bimetallic catalytic systems, with the possible adding of dopants as Sn [8-15] Ru appeared as the most efficient. Hernandez-Mejia et al.[16] reported that xylose can be selectively converted to xylitol in the presence of rutile phase TiO2 supported Ru (1 wt.%), despite the low surface area displayed by the rutile support. Authors then reported xylose yields higher than 90%, for a reaction performed in water at

Immense global generation of food waste calls for advanced technologies to maximize the use of such renewable carbon-based resources. In this study, corn, taro, lettuce, and bean sprout, were valorized for the production of value-added chemicals via sequential supercritical CO2 (scCO2) extraction and thermochemical conversion. The scCO2 extraction was performed at 350 bar and 50 °C for 60 min. The extracts of the lettuce contained sterols (764 μg g–1) that have potential anticancer properties. While bean sprout extracts had a higher content of saturated fatty acids (641 μg g–1), corn extracts comprised polyunsaturated fatty acids (405 μg g–1) as one of the major compounds, which are beneficial to cholesterol control. There were also notable amounts of wax esters (75–774 μg g–1) in these food waste extracts. Taro extracts were rich in both saturated (2313 μg g–1) and unsaturated fatty acids (1605 μg g–1) and, in particular, contained difatty acids that exhibit pharmaceutical activities. Moreover, the solid residues after scCO2 extraction served as the substrates for platform chemical production. The starch-rich substrates, i.e., taro and corn, resulted in 11–20% hydroxymethylfurfural (HMF) after microwave heating at 140 °C for 5–10 min using SnCl4 catalyst. In comparison, due to the high fiber content, lettuce and bean sprout required a higher temperature of 170–190 °C for chemical decomposition over H2SO4, generating a levulinic acid yield of ∼7%, in company with glucose and fructose as the coproducts. This study on the combined technologies suggested good compatibility between scCO2 extraction and subsequent thermochemical conversion, producing a wide spectrum of value-added chemicals from biomass waste. We herein highlight the vast potential of integrated technologies for food waste valorization in achieving sustainable and carbon-efficient biorefineries.

A series of organic acids, including maleic acid (maleicA), malic acid (malicA), succinic acid (SA), and oxalic acid (OA)/oxalate, was evaluated as green additives to promote the selective Al(III)-catalyzed production of hydroxymethylfurfural (HMF) from food waste. The roles of Al(III)–organic acid interactions in altering the catalytic functions were elucidated on the basis of experimental and computational evidence. The catalytic results showed that the Al/OA and Al/oxalate systems gave the slowest glucose conversion among the studied systems. OA/oxalate had such a high affinity for Al(III), that the Lewis acidity of Al(III) (i.e., ability to accept electron pairs) was unfavorably reduced, which was supported by the theoretical calculations of Gibbs free energies considering the Al(III)–OA complexes the most thermodynamically feasible. When rice waste was used as the substrate, which is rich in glucose-based starch, the addition of maleicA to the Al(III) system enhanced the HMF selectivity. The Lewis ac...

Les myopathies inflammatoires et dysimmunitaires (DIMs) touchent 14/100 000 personnes dans le monde. Ces pathologies sont classées par des critères immunopathologiques en quatre groupes : (1) polymyosites (PM)/ myosites à inclusions (IBM), (2) dermatomyosites, (3) myopathies nécrosantes auto-immunes et (4) myosites de chevauchement comprenant le syndrome anti-synthétase (ASS). Les ASS et PM/IBM sont caractérisées par la présence d’infiltrats inflammatoires mononucléés. Récemment, nous avons mis en évidence une expression myocytaire du complexe majeur d’histocompatibilité de type 2 (CMH2) dans les muscles de patients atteints d’ASS et d’IBM. L’expression du CMH2 est connue pour être induite par l’interféron-gamma (IFNγ) dans les cellules myogéniques. Or, les lymphocytes T CD8 (LTCD8), cellules productrices d’IFNγ sont retrouvés à proximité des fibres musculaires CMH2 positives. Cette cytokine inhibe la différenciation musculaire in vitro par l’interaction CIITA-myogénine (CIITA : major histocompatibility complex class II transactivator). Les mécanismes impliquant une toxicité musculaire médiée par les lymphocytes dans les DIMs restent inconnus. Les objectifs de ce projet sont dans un premier temps de caractériser les effets de l’IFNγ sur la biologie des cellules musculaires par des approches morphologiques, moléculaires et cellulaires. Puis, d’identifier le rôle de l’IFNγ dans ces myopathies et son impact au cours de la régénération musculaire. Des études préliminaires in vitro ont été réalisées sur des myoblastes humains et murins exposés ou non à l’IFNγ. Nos résultats devraient permettre d’obtenir de meilleures connaissances sur la physiopathologie des DIMs et d’identifier de potentielles nouvelles cibles thérapeutiques.

To investigate metal oxide surface catalysis, determining an appropriate Hubbard U-correction term is a challenge for the density functional theory (DFT) community and identifying realistic reactio...

The irradiation of concentrated feeds of carbohydrates in alcoholic solution by high-frequency ultrasound (550 kHz) induces the formation of alkylpolyglycosides (APGs). This work is distinct from previous reports in that it does not involve any (bio)catalyst or activating agent, it takes place at only 40 °C, thus avoiding degradation of carbohydrates, and it selectively yields APGs with a degree of polymerization in a window of 2¿7, an important limitation of the popular Fischer glycosylation. This ultrasound-based technology proved successful with a range of different valuable carbohydrates and alkyl alcohols. The elucidation of the structure of all the produced glycosides strongly suggests that 1,6-anhydrosugars formed in situ are key intermediate species., Authors are grateful to the CNRS, the University of Poitiers, the Ministry of Research, the Région Nouvelle Aquitaine, the MINECO (contract nos. SAF2016‐76083‐R and CTQ2015‐64425‐C2‐1‐R), the Junta de Andalucía (contract no. FQM2012‐1467) and the European Community (FEDER) for their financial supports.

An overview is provided on the recent advances in transglycosylation of cellulose and hemicellulose with either short-chain or long-chain alkyl alcohols. Catalytic processes are compared in terms of yield, selectivity and space-time yield, with a view to identifying the most promising pathways for future developments. In this context, the synthesis of alkylpolyglycosides directly from lignocellulosic biomass is discussed while keeping in mind the impact of the botanical origin on the transglycosylation reaction and the product distribution. A section dedicated to the physicochemical properties and ecological footprint of alkylpolyglycosides is also included.

L’analyse histologique du tissu musculaire est un élément déterminant pour le diagnostic et la compréhension physiopathologique des myopathies. Le développement d’outils numériques et informatiques permet des analyses d’images quantifiées à grande échelle applicable aux biopsies musculaires. L’analyse d’images automatisée permet de déterminer la taille de l’ensemble des myofibres sur un échantillon de muscle et d’évaluer l’atrophie myocytaire. Le codage couleur selon la taille permet de visualiser directement la topographie de l’atrophie myocytaire. Cette approche morphométrique appliquée à la dermatomyosite permettra une meilleure stratification des patients.

International audience; Herein, we describe an efficient and recyclable catalytic system based on metal triflates capable of converting highly concentrated feeds of furfuryl alcohol (30-40 wt %) to alkyl levulinates in excellent yields (>90%). This constitutes a unique and important advance in the field. Indeed, the dilution of feedstocks represent one of the major bottlenecks in catalysis for the industrial deployment of biobased fuels and chemicals in our society. The impact of water in the metal triflates catalytic performances is also discussed. A comparison with a commercialized process (SFOS) shows that this catalytic route is in line with industrial requirements in terms of yield, selectivity, reactor productivity, and capacity. In particular, unprecedented space time yields up to 200 kg m(-3) h(-1) were obtained.

This study aims to produce levulinic acid (LA) from paper towel waste in environment-friendly and economically feasible conditions, and evaluate the difference using solid and aqueous Bronsted acids. Direct dehydration of glucose to LA required sufficiently strong Bronsted acidity, where Amberlyst 36 demonstrated rapid production of approximately 30Cmol% of LA in 20min. However, the maximum yield of LA was limited by mass transfer. In contrast, the yield of LA gradually increased to over 40Cmol% in 1M H2SO4 at 150°C in 60min. The SEM images revealed the conversion in dilute acids under microwave at 150°C resulting in swelling structures of cellulose, which were similar to the pre-treatment process with concentrated acids. Further increase in reaction temperature to 200°C significantly shortened the reaction time from 60 to 2.5min, which saved the energy cost as revealed in preliminary cost analysis.

We reviewed the three reference toxicokinetic studies commonly used to suggestinnocuity of aluminum (Al)-based adjuvants. A single experimental study was carried out usingisotopic26Al (Flarend et al., 1997). This study ignored adjuvant cell capture. It was conductedover a short period of time (28 days) and used only two rabbits per adjuvant. At the endpoint,Al retention was 78% for aluminum phosphate and 94% for aluminum hydroxide, both resultsbeing incompatible with quick elimination of vaccine-derived Al in urines. Tissue distributionanalysis omitted three important retention sites: the injected muscle, the draining lymph nodeand bone. Two theoretical studies have evaluated the potential risk of vaccine Al in infants, byreference to the oral Minimal Risk Level (MRL) extrapolated from animal studies. Keith et al.,2002 used a too high MRL (2 mg/kg/d), an erroneous model of 100% immediate absorptionof vaccine Al, and did not consider renal and blood-brain barrier immaturity. Mitkus et al.(2011) only considered absorbed Al, with erroneous calculations of absorption duration. Theyignored particulate Al captured by immune cells, which play a role in systemic diffusion andthe neuro-inflammatory potential of the adjuvant. MRL they used was both inappropriate (oralAl vs injected adjuvant) and far too high (1 mg/kg/d) with regard to experimental studiesof Al-induced memory and behavioral changes. Both paucity and serious weaknesses of thesestudies strongly suggest that novel experimental studies of Al adjuvants toxicokinetics shouldbe performed on the long-term, including post-natal and adult exposures, to ensure innocuityand restore population confidence in Al-containing vaccines., Dans le prolongement de la réflexion menée par l’Académie nationale de pharmacienous avons réévalué les 3 études de référence suggérant l’innocuité des adjuvants alumi-niques. Une seule étude expérimentale a été menée grâce à l’26Al isotopique (Flarend et al.,1997). Cette étude, ignorant la capture cellulaire des adjuvants et menée pendant 28 jours surseulement 2 lapins par adjuvant, a montré une rétention de 78 % de l’Al de l’adjuvant phos-phate de 94 % de l’hydroxyde. Ces résultats sont incompatibles avec une élimination rapidede l’aluminium vaccinal par voie urinaire. L’étude de la distribution tissulaire a omis le muscleinjecté, le ganglion de drainage, et l’os. Deux études théoriques ont calculé le risque de l’Alvaccinal chez le nourrisson, par référence au Minimal Risk Level (MRL) par voie orale extra-polé d’expériences animales. Keith et al. (2002) ont utilisé un MRL trop élevé (2 mg/kg/j), unmodèle erroné d’absorption immédiate de 100 % de l’Al vaccinal, et n’ont pas tenu compte del’immaturité du rein et de la barrière hémato-encéphalique. Mitkus et al. (2011) ne considérantque l’Al absorbé ont ignoré l’Al particulaire dont la capture par les cellules immunitaires joueun rôle dans la migration systémique et le potentiel neuro-inflammatoire de l’adjuvant. Son utilisation d’un MRL par voie orale est inapproprié et d’un niveau (1 mg/kg/j) bien trop élevé auregard des travaux expérimentaux récents. Les durées d’absorption calculées sont inexactes.Ces faiblesses conceptuelles et méthodologiques rendent souhaitable la réalisation de nouvellesétudes toxicocinétiques expérimentales de long terme afin que soit garanti l’innocuité desadjuvants à base d’aluminium.

The review describes the most significant recent results achieved in France in the field of heterogeneous catalysis over the last 10 years. It focusses on the research carried out in the French academic laboratories, often in close collaboration with some industrial partners.

INTRODUCTION Patients with renal failure who are being treated with dialysis frequently develop neuromuscular manifestations. Renal failure-associated calciphylaxis, also termed calcific uremic arteriolopathy (CUA), is a life-threatening condition usually observed in patients with end-stage renal disease on chronic dialysis or after renal transplantation. METHODS We describe a hemodialyzed patient who presented with rapidly progressive unexplained systemic vasculopathy, muscle atrophy, and proximal weakness, that unexpectedly proved to be caused by calciphylaxis. RESULTS Quadriceps muscle biopsy disclosed diffuse vascular calcific deposits on medium- and small-sized vessels, characteristic of CUA. Other changes included ischemic myopathy, focal intracellular calcium accumulation within myofibers, and calcium deposits in endomysial capillaries associated with marked complement activation and C5b9 formation. CONCLUSION There are only a few descriptions of muscle involvement in the context of CUA, a condition with a prognosis that depends on early diagnosis and treatment. This report underscores the usefulness of muscle biopsy in the diagnosis of systemic calciphylaxis. Muscle Nerve 56: 529-533, 2017.

Resume Objectifs Les adjuvants vaccinaux contenant de l’aluminium permettent une reponse adequate de l’organisme a la vaccination. L’innocuite et l’elimination rapide de ces molecules, gages de leur utilisation en toute securite depuis plusieurs decennies, sont discutees dans un nombre d’etudes croissant depuis 20 ans. L’evaluation de l’exposition aux adjuvants aluminiques semble ainsi essentielle. La revue qui suit repond aux questions suivantes : quelle est l’exposition en adjuvants aluminiques pour un individu vaccine en France ? Quels sont les facteurs de variation ? Methodes Pour evaluer la quantite cumulee d’aluminium vaccinal a laquelle un individu peut etre desormais expose en France, nous avons utilise le calendrier vaccinal 2018 et la base de donnees de la securite sociale pour les vaccins rembourses cette annee-la. Seuls les vaccins obligatoires et recommandes en France pour un individu ne voyageant pas a l’etranger et sans obligations professionnelles particulieres ont ete pris en compte. Resultats Nos resultats montrent qu’un individu qui suit les obligations et recommandations vaccinales de 2018, recevra entre 2545 et 7735 μg d’Al3+ au cours de sa vie, dont au moins 50 % avant l’âge d’un an. L’exposition varie en fonction de l’âge, du poids, du sexe et des choix des vaccins administres. Conclusion Les doses les plus importantes de sels d’aluminium sont majoritairement injectees en debut de vie. Les femmes recoivent une dose proportionnellement plus importante que les hommes. Les vaccins les plus rembourses sont souvent ceux comportant la plus grande quantite d’aluminium.

International audience; In this study, Pd-based catalytic model hosted over nitrogen enriched fibrous Porous-Organic-Polymer (POP) is established to execute hydrodeoxygenation of various vegetable oils in producing potential large-scale renewable diesel. Here we report a cost effective synthesis strategy of a new microporous hypercrosslinked POP through the FeCl3 assisted Friedel-Crafts alkylation reaction, followed by fabrication of Pd 0-NPs (2-3 nm) with solid gas phase hydrogenation route to deliver a novel catalytic system. This catalyst (called Pd@PPN) exhibits versatile catalytic performance for different types of vegetable oils including palm oil, soybean oil, sunflower oil and rapeseed oil to furnish long chain diesel range alkanes. The catalyst is comprehensively characterized by various spectroscopic tools and shows high stability during five runs of recycling without the leaching of Pd occuring. Our results further reveal that direct decarbonylation (DCN) pathway of fatty acid to produce alkanes with one carbon less is the dominated mechanism. At optimized conditions, using stearic acid to represent the long linear carboxylic acids in the vegetable oils, up to 90 % conversion with 83 % selectivity of C17-alkane has been achieved on our fabricated catalyst. Density functional theory (DFT) calculations are performed to provide insights into the electronic properties of the catalyst, the mechanistic reaction pathway, the crucial role of catalyst surface and the product selectivity trend. The strong interaction between corrugated polymer-frame-structure and the Pd-NPs suggests there is the presence of high density step sites on the fabricated Pd-NP anchored within the cage of polymer structure. DFT calcualtions also reveal the strong promotional effect of step sites and charge transfer in facilitating rate-limiting steps during the decarbonylation (DCN) pathway and removal of strongly bound intermediates formed during the process, therefore explain the high activity of the fabricated Pd@PPN catayst for the hydrodeoxygenation (HDO) conversion to produce bio-based alkanes diesel.

International audience; The production of amino-containing compounds from biomass is an important goal of research programs. Starting from carbohydrate-based furfural, a simple and highly efficient system was developed for producing a library of secondary and tertiary tetrahydrofurfurylamines under mild conditions (25 °C/1 bar H2) with excellent yields (>90%). Commercially available Pd/Al2O3 proved to be a suitable catalyst and exhibited outstanding performance.

Dysferlinopathies belong to the heterogeneous group of autosomal recessive muscular disorders, caused by mutations in the dysferlin gene and characterized by a high degree of clinical variability even though within the same family. This study aims to describe three cases, belonging to a consanguineous Tunisian family, sharing a new splicing mutation in the dysferlin gene and presenting intra-familial variability of dysferlinopathies: Proximal–distal weakness and distal myopathy with anterior tibial onset. We performed the next generation sequencing for mutation screening and reverse transcriptase-PCR for gene expression analysis. Routine muscle histology was used for muscle biopsy processing. The clinical presentation demonstrated heterogeneous phenotypes between the three cases: Two presented intermediate phenotypes of dysferlinopathy with proximal–distal weakness and the third had a distal myopathy with anterior tibial onset. Genetic analysis yielded a homozygous splicing mutation (c.4597-2A>G) in the dysferlin gene, giving rise to the suppression of 28 bp of the exon 43. The splicing mutation found in our family (c.4597-2A>G) is responsible for the suppression of 28 bp of the exon 43 and a wide clinical intra-familial variability.

Macroautophagy (hereafter referred to as autophagy) is an evolutionarily conserved catabolic process whose loss-of-function has been linked to a growing list of pathologies. Knockout mouse models of key autophagy genes have been instrumental in the demonstration of the critical functions of autophagy, but they display early lethality, neurotoxicity and unwanted autophagy-independent phenotypes, limiting their applications for in vivo studies. To avoid problems encountered with autophagy-null transgenic mice, we investigated the possibility of disturbing autophagy pharmacologically in the long term. Hydroxychloroquine (HCQ) ip injections were done in juvenile and adult C57bl/6j mice, at range doses adapted from the human malaria prophylactic treatment. The impact on autophagy was assessed by western-blotting, and juvenile neurodevelopment and adult behaviours were evaluated for four months. Quite surprisingly, our results showed that HCQ treatment in conditions used in this study neither impacted autophagy in the long term in several tissues and organs nor altered neurodevelopment, adult behaviour and motor capabilities. Therefore, we recommend for future long-term in vivo studies of autophagy, to use genetic mouse models allowing conditional inhibition of selected Atg genes in appropriate lineage cells instead of HCQ treatment, until it could be successfully revisited using higher HCQ doses and/or frequencies with acceptable toxicity.

Furfural is a platform molecule obtained from hemicellulose. Among the products that can be produced from furfural, furfuryl alcohol is one of the most extensively studied. It is synthesized at an industrial scale in the presence of CuCr catalyst, but this process suffers from an environmental negative impact. Here, we demonstrate that a non-noble metal catalyst (Co/SiO2) was active (100% conversion of furfural) and selective (100% selectivity to furfuryl alcohol) in the hydrogenation of furfural to furfuryl alcohol at 150 °C under 20 bar of hydrogen. This catalyst was recyclable up to 3 cycles, and then the activity decreased. Thus, a comparison between batch and continuous flow reactors shows that changing the reactor type helps to increase the stability of the catalyst and the space-time yield. This study shows that using a continuous flow reactor can be a solution to the catalyst suffering from a lack of stability in the batch process.

The depolymerization of cellulose to glucose is a challenging reaction and often constitutes a scientific obstacle in the synthesis of downstream bio-based products. Here, we show that cellulose can be selectively depolymerized to glucose by ultrasonic irradiation in water at a high frequency (525 kHz). The concept of this work is based on the generation of H˙ and ˙OH radicals, formed by homolytic dissociation of water inside the cavitation bubbles, which induce the cleavage of the glycosidic bonds. The transfer of radicals on the cellulose particle surfaces prevents the side degradation of released glucose into the bulk solution, allowing maintaining the selectivity to glucose close to 100%. This work is distinguished from previous technologies in that (i) no catalyst is needed, (ii) no external source of heating is required, and (iii) the complete depolymerization of cellulose is achieved in a selective fashion. The addition of specific radical scavengers coupled to different gaseous atmospheres and ˙OH radical dosimetry experiments suggested that H˙ radicals are more likely to be responsible for the depolymerisation of cellulose., Ultrasonic irradiation of cellulose at a high frequency induces its selective depolymerization to glucose at room temperature and atmospheric pressure within only a few minutes.

The selective hydroconversion of 5‐hydroxymethylfurfural (HMF) to biofuels is currently highly sought‐for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non‐promoted Ni/SBA‐15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5‐dimethylfuran (DMF) and to 2,5‐dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5‐methylfurfural (MFFR) as intermediate, though the route via 2,5‐bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates. 12;7

Méthode automatisée d’analyse d’images appliquée à la dermatomyosite.L’analyse histologique du tissu musculaire est un élément déterminant pour le diagnostic et la compréhension physiopathologique des myopathies. Le développement d’outils numériques et informatiques permet des analyses d’images quantifiées à grande échelle applicable aux biopsies musculaires. L’analyse d’images automatisée permet de déterminer la taille de l’ensemble des myofibres sur un échantillon de muscle et d’évaluer l’atrophie myocytaire. Le codage couleur selon la taille permet de visualiser directement la topographie de l’atrophie myocytaire. Cette approche morphométrique appliquée à la dermatomyosite permettra une meilleure stratification des patients.

Here we report the oxidative dehydrogenation of malic acid to oxaloacetic acid, a key precursor in the fabrication of amino acids, over Pt–Bi/C catalysts. Under optimized conditions, we discovered that OAA was selectively produced with up to 60% conversion (i.e. 60% yield). The recurrent unwanted decarboxylation of OAA to pyruvic acid was circumvented by successfully conducting the catalytic reaction at 25 °C. A comparison with the classical Fenton oxidation reaction is discussed.

Quinaldic acids are important fine chemicals. Nowadays, industrial methods to synthesize quinaldic acids rely heavily on a three-step process established based on the Reissert reaction, which involves however the use of highly toxic potassium cyanide. In this paper, a novel cyclization of aniline with ethyl 4,4-diethoxycrotonate was realized, which offered ethyl quinaldate in good yield. Based on this reaction, an eco-efficient method to prepare quinaldic acids was developed, which involves the following three steps: (i) synthesis of ethyl 4,4-diethoxycrotonate through photooxidation of furfural and a consecutive ring-opening alcoholysis; (ii) cyclization of ethyl 4,4-diethoxycrotonate with aniline, and (iii) hydrolysis of the generated ethyl quinaldate. This new method not only avoids the use of toxic potassium cyanide but also meets many salient features of green chemistry, such as the use of bio-based feedstocks, environmentally benign metal-free conditions and good reaction yields.