Les polyazacycloalcanes sont largement utilisés pour l’élaboration de radiopharmaceutiques destinés à la médecine nucléaire. Ces structures, et plus particulièrement celles dérivées du cyclam, permettent une complexation idéale du cuivre et ainsi une application en imagerie TEP, avec l’utilisation du 64Cu, ou en radiothérapie grâce à l’isotope 67Cu. Le cyclam doit, en plus d’être N-fonctionnalisé par des bras coordinants, disposer d’une fonction supplémentaire permettant la bioconjugaison à une biomolécule pour un ciblage spécifique des cellules cancéreuses. Une première partie de cette thèse a porté sur la synthèse du cyclam monopicolinate C-fonctionnalisé par une fonction de bioconjugaison de type benzyle isothiocyanate. Cette synthèse, basée sur des travaux antérieurs du laboratoire, a nécessité la mise au point d’une méthode d’alkylation régiospécifique du cyclam C-fonctionnalisé par le biais de protections sélectives des atomes d’azote du macrocycle. Le ligand a ensuite été étudié in vitro et in vivo, par nos collaborateurs nantais du CRCINA, pour l’imagerie immuno-TEP du myélome multiple.La seconde partie de ce travail s’est consacrée à l’élaboration d’un dérivé polyfonctionnel du cyclam possédant deux fonctions permettant le ciblage des cellules tumorales. Ce composé a été synthétisé au sein du laboratoire brestois puis étudié, in vitro et in vivo, dans les locaux de la NECSA en Afrique duSud pour l’imagerie TEP du cancer du sein.Ces deux projets ont permis d’obtenir une preuve de concept en imagerie TEP ce qui confirme le potentieldes ligands dérivés de cyclam C-fonctionnalisés pour l’élaboration de radiopharmaceutiques à base de cuivre pour la médecine nucléaire. / Polyazacycloalkanes are wildly used in the conception of radiopharmaceuticals for nuclear medicine. These structures, and especially cyclam derivatives, provide ideal complexation properties of copper, which can be applied in nuclear medicine applications with the 64Cu isotope for PET imaging or with 67Cu for radiotherapy purpose. Cyclams derivatives have to be N-functionalized with coordinative arms, and moreover include an additional function especially introduced for the bioconjugation of a biomolecule in the aim to preferentially target cancer cells.The first project treated in this manuscript consisted of the synthesis of a monopicolinate cyclam C-functionalized with a benzyl isothiocyanate function for the bioconjugation. Based on precedent results obtained in the Lab, a regiospecific alkylation method has been developed for the synthesis of this ligand.This method implies the selective protection and deprotection of the macrocycle nitrogen atoms. This ligand, once obtained, has been studied in vitro and in vivo, by our collaborators of the CRCINA in Nantes, for multiple myeloma immuno-PET imaging.The second project of this work is dedicated to the conception of a radiopharmaceutical based on apolyfunctionnal cyclam which bear two different moieties allowing the targeting of cancer cells. This ligand has been synthesized in our Lab in Brest and studied, in vitro and in vivo, in the South African NECSA company for breast cancer PET imaging.These two projects were elaborated in the aim to obtain a proof of principle in PET imaging and to confirm the high potential of C-funcitonnalized cyclam derivatives for nuclear medicine applications.

Dimethylether is a non-toxic liquefied gas, which is projected to become one of the fundamental chemical feedstock in the future. Dimethylether can be produced from syngas via a two-step (indirect) process that involves synthesis of methanol by hydrogenation of CO/CO2 over a copper based catalyst and subsequent dehydration of methanol to DME over an acidic catalyst. Alternatively, DME can be produced in an one-step (direct) process using a hybrid (bifunctional) catalyst system that permits both methanol synthesis and dehydration in a single process unit. In the present research work the production of DME has been studied by applying both the indirect and direct processes. Firstly, the methanol synthesis and methanol dehydration reactions involved in the indirect process have been studied separately. Afterwards, these two reactions have been combined in the direct DME production process by using a hybrid catalyst comprising a methanol synthesis and a methanol dehydration component. The methanol synthesis by CO2 hydrogenation has been investigated over commercial and home-made CuO/ZnO/Al2O3 catalysts with the aim to identify optimal experimental conditions (CO2:H2 ratio, flow rate, temperature) that could be then used in the direct conversion of CO2/H2 mixtures into methanol/DME. Obtained results reveal that the conversion of CO2 and the yields of reaction products (CH3OH and CO) increase when the concentration of H2 in the feed and the reaction contact time are increased. It was found that both Cu+/Cu0 species are important for the conversion of CO2/H2, although the presence of Cuo seems to be more important for selectivity/yield of methanol. The stability of the CuO/ZnO/Al2O3 catalyst has been also investigated. It was observed that the main reason for the deactivation of catalyst is the water produced via the methanol synthesis and reverse water gas shift reactions. However, the catalytic activity and products selectivity were recovered slowly to their original levels after applying a regeneration procedure, indicating that deactivation by water is reversible. The dehydration of methanol to dimethylether (DME) has been investigated over a range of catalysts including alumina, silica-alumina and zeolites with different physicochemical characteristics. The effects of temperature and the presence of water vapour in the feed on catalytic performance have been studied in detail. The reactivity of catalysts has been evaluated by determining the reaction rates per gram of catalyst per acid site (total: Brönsted+Lewis) and per Brönsted/Lewis mole ratio. In addition, the reaction mechanism has been investigated over a selected catalyst, with the use of transient-MS and in situ DRIFTS techniques. Results obtained for alumina catalysts show that the catalytic activity and selectivity are determined to a large extent by the textural properties, degree of crystallinity and total amount of acid sites of catalysts. In particular, the methanol conversion curve shifts toward lower reaction temperatures with an increase of specific surface area. However, the enhanced catalytic activity of high-SSA samples cannot be attributed solely to the higher amount of surface acid sites, implying that the reaction rate is determined to a large extent from other parameters, such as textural properties and degree of crystallinity. Results of mechanistic studies indicate that interaction of methanol with the Al2O3 surface results in the formation of two kinds of methoxy groups of different adsorption strength. Evidence is provided that DME evolution is associated with methoxy species that are weakly adsorbed on the Al2O3 surface, whereas more strongly held species decompose to yield surface formate and, eventually, CH4 and CO in the gas phase. Results obtained over zeolite catalysts show that catalytic performance depends on the topology of zeolites due to differences in micropore structure and Si/Al ratio as well as on the number, strength and nature of active acid sites. The activity of zeolite catalysts for the methanol dehydration to DME follows the order ZSM-5 > Ferrierite > Mordenite ~ Beta ~ USY > H-Y. The strong Brönsted acid sites of ZSM-5 zeolites with relatively high Si/Al ratio represent the most active sites in methanol dehydration to DME reaction. However, the overall reactivity of the ZSM-5 zeolites is also affected by the balance of the Brönsted to Lewis acid sites. The activity of Beta and USY zeolites is determined by both Lewis and Brönsted acid sites. The moderate/low reactivity of Ferrierite, Mordenite and H-Y zeolite are determined by the abundant Brönsted acid sites of relatively weak/moderate strength. The direct CO2 hydrogenation to methanol/DME has been investigated using admixed catalysts comprising a methanol synthesis (commercial copper based catalyst: CZA1) and a methanol dehydration component (different alumia/zeolite catalysts: γ-Al2O3, ZSM-5, W/γ-Al2O3, USY(6), Ferrierite(10)). It has been revealed that the conversion of CO2 is always lower than the corresponding equilibrium values predicted by thermodynamics, indicating operation in the kinetic regime. The nature of the methanol dehydration component of the admixed catalysts was found to be important for both CO2 conversion and methanol dehydration. In particular, DME selectivity/yield, depends strongly on the nature of acid sites (both Lewis and Brönsted) as well as the textural (meso/macro porosity) and topological properties of methanol dehydration component of the admixed catalysts. The yield of DME obtained at a temperature of 250oC decreases following the order CZA1/ZSM-5, CZA1/USY(6) > CZA1/Ferrierite(10) > CZA1/ W/γ-Al2O3 >> CZA1/γ-Al2O3. The long-term stability experiments conducted over selected bifunctional catalytic systems revealed that the catalysts deactivate with time-on-stream, mainly due to water produced via methanol synthesis, methanol dehydration and reverse water gas shift reactions. In case of the CZA1/ZSM-5 admixed catalyst the catalytic activity and products selectivity were almost recovered after regeneration indicating that deactivation by water is reversible. / --

No description available.

Late transition metal complexes of silver(I), rhodium(I), ruthenium(II), palladium(II) and platinum(II) containing a nitrile-functionalized N-heterocyclic carbene ligand (C-CN) were prepared. The nitrile group on the C–CN ligand was shown to undergo hydrolysis under basic conditions, leading to a silver(I) carbene complex with a primary-amido functional group, and a trimetallic complex of palladium(II) with a partially hydrolyzed C–N–N–C donor ligand. The reduction of a nitrile-functionalized imidazolium salt in the presence of nickel(II) chloride under mild conditions yielded an axially chiral square-planar nickel(II) complex containing a unique primary-amino functionalized N-heterocyclic carbene ligand (C-NH2). A transmetalation reaction moved this chelating C–NH2 ligand from nickel(II) to ruthenium(II), osmium(II), and iridium(III), yielding important catalysts for the hydrogenation of polar double bonds. The ruthenium(II) complex, [Ru(p-cymene)(C–NH2)Cl]PF6 catalyzed the transfer and H2-hydrogenation of ketones. The bifunctional hydride complex, [Ru(p-cymene)(C–NH2)H]PF6, which contains a Ru–H/N–H couple showed no activity under catalytic conditions unless when activated by a base. The outer-sphere mechanism involving bifunctional catalysis of ketone reduction is disfavored according to experimental and theoretical studies and an inner-sphere mechanism is proposed involving the decoordination of the amine donor from the C–NH2 ligand. The ruthenium(II) complex [RuCp*(C–NH2)py]PF6 showed higher activity than the iridium(III) complex [IrCp*(C–NH2)Cl]PF6 in the hydrogenation of ketones. This ruthenium(II) complex also catalyzes the hydrogenation of an aromatic ester, a ketimine, and the hydrogenolysis of styrene oxide. We proposed an alcohol-assisted outer sphere bifunctional mechanism for both systems based on experimental findings and theoretical calculations. The cationic iridium(III) hydride complex, [IrCp*(C–NH2)H]PF6 , was prepared and this failed to react with a ketone in the absence of base. The crucial role of the alkoxide base was demonstrated in the activation of this hydride complex in catalysis. Calculations support the proposal that the base deprotonates the amine group of this hydride complex and triggers the migration of the hydride to the η5-Cp* ring producing a neutral iridium(I) amido complex. This system contains an active Ir–H/N–H couple required for the outer sphere hydrogenation of ketones in the bifunctional mechanism.

Late transition metal complexes of silver(I), rhodium(I), ruthenium(II), palladium(II) and platinum(II) containing a nitrile-functionalized N-heterocyclic carbene ligand (C-CN) were prepared. The nitrile group on the C–CN ligand was shown to undergo hydrolysis under basic conditions, leading to a silver(I) carbene complex with a primary-amido functional group, and a trimetallic complex of palladium(II) with a partially hydrolyzed C–N–N–C donor ligand. The reduction of a nitrile-functionalized imidazolium salt in the presence of nickel(II) chloride under mild conditions yielded an axially chiral square-planar nickel(II) complex containing a unique primary-amino functionalized N-heterocyclic carbene ligand (C-NH2). A transmetalation reaction moved this chelating C–NH2 ligand from nickel(II) to ruthenium(II), osmium(II), and iridium(III), yielding important catalysts for the hydrogenation of polar double bonds. The ruthenium(II) complex, [Ru(p-cymene)(C–NH2)Cl]PF6 catalyzed the transfer and H2-hydrogenation of ketones. The bifunctional hydride complex, [Ru(p-cymene)(C–NH2)H]PF6, which contains a Ru–H/N–H couple showed no activity under catalytic conditions unless when activated by a base. The outer-sphere mechanism involving bifunctional catalysis of ketone reduction is disfavored according to experimental and theoretical studies and an inner-sphere mechanism is proposed involving the decoordination of the amine donor from the C–NH2 ligand. The ruthenium(II) complex [RuCp*(C–NH2)py]PF6 showed higher activity than the iridium(III) complex [IrCp*(C–NH2)Cl]PF6 in the hydrogenation of ketones. This ruthenium(II) complex also catalyzes the hydrogenation of an aromatic ester, a ketimine, and the hydrogenolysis of styrene oxide. We proposed an alcohol-assisted outer sphere bifunctional mechanism for both systems based on experimental findings and theoretical calculations. The cationic iridium(III) hydride complex, [IrCp*(C–NH2)H]PF6 , was prepared and this failed to react with a ketone in the absence of base. The crucial role of the alkoxide base was demonstrated in the activation of this hydride complex in catalysis. Calculations support the proposal that the base deprotonates the amine group of this hydride complex and triggers the migration of the hydride to the η5-Cp* ring producing a neutral iridium(I) amido complex. This system contains an active Ir–H/N–H couple required for the outer sphere hydrogenation of ketones in the bifunctional mechanism.

Deux zéolithes nanocristaux de type *BEA et CP814E commerciales avec de différentes propriétés texturales, et une zéolithe microcristaux de type *BEA qui a été synthétisée durant cette thèse, ont été modifiées par une desilication en utilisant de différents traitements alcalins. Toutes les zéolithes parentes et certaines désilicées ont été sélectionnée pour le craquage du n-hexane, où aucune amélioration significative de la conversion n'a été observée après la désilication. Toutes les zéolithes parentes et quelques désilicées sélectionnées ont été transformés en leur forme bifonctionnelle par imprégnation du platine pour d'étudier l'impact de la désilication dans l'hydroisomérization de n-C10. On a constaté que l'amélioration des propriétés texturales par la désilication n'était pas toujours la cause d'une augmentation ou d'une diminution de l'activité et de la sélectivité du catalyseur, mais plutôt de la localisation des particules de Pt et leur distance prédite des sites acides. Cependant, la présence des mésopores inter- et intracristallins, en plus de la distance de Pt-H+, sont des importants caractéristiques qui affectent l'activité et la sélectivité. Nous avons également étudié l'impact de la longueur de chaîne dans l'hydroisomérization de n-C12 et de n-C14. Un phénomène spécial dans le cas de n-C12 est apparu, où le rendement d'isomérisation semblait inférieur à celui obtenu sur n-C10 et n-C14, ce qui suggère que cela résulte de l'effet de confinement. La série microcristaux a montré une amélioration de l'activité dans la transformation n-C14, mais une diminution de la sélectivité des isomères à cause des limites de diffusion potentielles. / Two commercial nanocrystal *BEA zeolites with different textural properties and a microcrystal synthesized *BEA zeolite, were desilicated using different alkaline treatment; classical in presence of Noah alone, or incorporated with a pore directing agent. All parent zeolites and some selected desilicated samples were chosen for catalytic cracking of n-hexane, where no significant improvement of n-hexane conversion was observed after desilication. To investigate the impact of desilication on the hyrdoisomerization of n-C10, all parent and the some selected desilicated zeolites were transformed into their bifunctional form by platinum loading. The improvement of the textural properties by desilication using the different pore directing agents, was not always the cause behind an increase or decrease in the activity and selectivity of the catalyst, but rather was more the location of the Pt particles and their predicted distance from the acidic sites. However, the synergetic effect of both the textural and bifunctional characteristics was positive. Tests on hydroisomerization of n-C12 and n-C14 to investigate the impact of chain length were done. In the nanocrystal series, a special phenomenon on n-C12 appeared where the isomerization yield seemed to be less than that obtained on n-C10 and n-C14, suggesting that this would be due the confinement effect, which was shown to be more effective in case of n-C12. The microcrystal series showed an improvement of the activity over all the catalysts in case of n-C14 transformation, but a decrease in isomers selectivity as observed due to probable diffusional limitations within the channels of these series catalysts.

Au cours de ce travail de nouvelles méthodes pour la formation de liaison C-N ont été développées. Dans la première partie de cette thèse une application de catalyse métal-ligand bifonctionnelle pour la réaction énantiosélective aza-Michael est démontrée. Dans la deuxième partie nous présentons le travail sur les cyclisations, en utilisant des alcaloïdes du quinquina facilement disponibles, comme catalyseurs des plus prometteurs, fournissant des β-amino-acides d’indoline avec jusqu'à 98% ee. Parmi eux, l’hydroquinidine ressort du lot comme étant le catalyseur donnant le meilleur excès énatiomérique. La troisième partie est liée à l'élaboration d'un nouveau processus intermoléculaires de diamination de styrènes, diènes et triènes, utilisant des bis-sulfonylimides comme source d'azote, en combinaison avec le diacétate de iodosobenzène, qui fournit une approche intéressante et efficace de diamines vicinales biologiquement et chimiquement important. La réaction peut être effectuée à température ambiante sans avoir besoin de protection par atmosphère inerte. / The concept of metal-ligand bifunctionality was successfully applied for an enantioselective aza-Michael reaction by employing well-defined ruthenium amido complexes. The catalyst was optimised and the corresponding chiral indoline β-amino acid derivatives were obtained with high enantioselectivities. Next, a straightforward enantioselective bifunctional organocatalytic approach was also developed. Employing hydroquinidine as catalyst the corresponding cyclic products were obtained in excellent enantioselectivities and quantitative yields. These compounds can be selectively deprotected and applied to peptide synthesis. Finally, we have developed unprecedented diamination reactions of styrenes, butadienes and hexatrienes employing easily accessible hypervalent iodine(III) reagents under robust reaction conditions. The first examples of the metal-free 1,2-diamination of butadienes were demonstrated and this oxidation methodology was further extended to the highly attractive 1,4 installation of two nitrogen atoms within a single step.

Une bibliothèque de nouveaux catalyseurs bifonctionnels combinant à la fois l’aminocatalyse et l’activation acide par un acide phosphonique sur une même structure peptidique a été développée. Des variations structurales ont été apportées afin d’optimiser la géométrie du site catalytique. Le potentiel de ces catalyseurs a été testé sur la réaction d’addition de Michael stéréosélective d’aldéhydes sur divers nitroalcènes aromatiques. Dans des conditions optimisées, de très bonnes sélectivités (r.d. < 95:5 / r.e. < 93:7) ont été atteintes. Grâce à leur forte solubilité dans l’eau, ces catalyseurs ont été facilement extraits et réutilisés sur 10 cycles sans perte significative de sélectivité. Enfin, des études mécanistiques ont été menées afin de connaitre le mode d’action exact de ces catalyseurs. Tant l’énamine que l’activation acide se sont avérées essentielles pour que la réaction ait lieu. L’enchainement peptidique permet une réaction intramoléculaire et stéréosélective. / A novel bifunctional organocatalyst library combining both aminocatalysis and phosphonic acid activation on a peptide structure was developed. Some structural variations allowed the optimization of the catalytic site. The potential of these catalysts was evaluated on the stereoselective Michael addition of aldehydes with several aromatic nitroalkenes. In optimized conditions, very good selectivities (up to 95:5 d.r. and 93:7 e.r) were achieved. Due to their high water-solubility, the catalysts were easily recyclable and reused over several cycles without any significant loss of selectivities. Mechanistic investigations were carried out to understand the exact mode of action of the catalysts. Both enamine formation and acid activation were essential for the reaction to occur. The peptide structure allows an intramolecular and stereoselective reaction.

Made available in DSpace on 2014-12-17T14:03:28Z (GMT). No. of bitstreams: 1 LudovicoM.pdf: 1651172 bytes, checksum: 32d873e29ab629d06ae3a79806c6523e (MD5) Previous issue date: 2008-07-02 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Serines proteinases inhibitors (PIs) are widely distributed in nature and are able to inhibit both in vitro and in vivo enzymatic activites. Seed PIs in than leguminous are classified in seven families, Bowman-Birk and Kunitz type families that most studied representing an important role in the first line of defense toward insects pests. Some Kunitz type inhibitors possess activities serine and cysteine for proteinases named bifunctional inhibitor, as ApTKI the inhibitor isolate from seed of Adenanthera pavonina. The A. pavonina inhibitor presenting the uncommon property and was used for interaction studies between proteinases serine (trypsin) and cysteine (papain). In order to determinate the in vitro interaction of ApTKI against enzymes inhibitor purification was carried cut by using chromatographic techniques and inhibition assays. The 3D model of the bifunctional inhibitor ApTKI was constructed SWISS-MODEL program by homology modeling using soybean trypsin inhibitor (STI, pdb:1ba7), as template which presented 40% of identity to A. pavonina inhibitor. Model quality was evaluated by PROCHECK program. Moreover in silico analyzes of formed complex between the enzymes and ApTKI was evaluated by HEX 4.5 program. In vitro results confirmed the inhibitory assays, where the inhibitor presented the ability to simultaneously inhibit trypsin and papain. The residues encountered in the inhibitor model of folder structural three-dimensional that make contact to enzymes target coud explain the specificity pattern against serine and cysteine proteinases / Os inibidores de proteinases ser?nicas (IPs) est?o extensamente distribu?dos na natureza e inibem a atividade enzim?tica in vitro e in vivo. Estes IPs em sementes de leguminosas compreendem sete fam?lias, no entanto as fam?lias Bowman-Birk e do tipo Kunitz s?o as mais estudadas e representam um papel importante na primeira linha de defesa contra insetos pragas. Alguns inibidores do tipo Kunitz possuem atividades para proteinases ser?nicas e ciste?nicas sendo denominados inibidores bifuncionais, como o inibidor ApTKI da semente de Adenanthera pavonina. O inibidor de A. pavonina por apresentar essa caracter?stica incomum aos inibidores dessa fam?lia foi utilizado para o estudo da intera??o entre as proteinases ser?nica (tripsina) e ciste?nica (papa?na). Para determinar a intera??o in vitro de ApTKI e as enzimas alvo foi realizada a purifica??o do inibidor a partir de t?cnicas cromatogr?ficas e ensaios de inibi??o. O modelo 3D do inibidor bifuncional ApTKI foi constru?do pelo programa SWISS-MODEL atrav?s da metodologia de modelagem por homologia utilizando como molde o inibidor de tripsina de soja (STI, pdb:1ba7) que apresentou 40% de identidade com a prote?na alvo. A qualidade do modelo foi avaliada pelo programa PROCHECK. Para a an?lise do complexo in silico entre as enzimas alvo e o inibidor foi utilizado o programa HEX 4.5. Estes resultados confirmaram os ensaios inibit?rios in vitro, onde ApTKI apresentou a capacidade de inibir simultaneamente tripsina e papa?na. Algumas das diferen?as observadas nos res?duos do sitio reativo explicam a forte afinidade para tripsina e a fraca para papa?na

Dans le contexte de la valorisation des bioressources, l'hydrogénolyse sélective du glycérol en composé C3 (propanediols, propanol, propane) est étudiée en phase aqueuse sur des catalyseurs bifonctionnels à base de ruthénium, seul ou modifié par ajouts d'étain, ou à base de platine, supportés sur alumine, alumine-silice ou oxyde de titane. Les ajouts d'étain sont effectués par différentes méthodes : co-imprégnation, imprégnation successive et réduction catalytique. La réaction d'hydrogénolyse du glycérol est réalisée en autoclave, à 210°C, P=60 bar (sous N2 ou H2), avec une solution aqueuse à 4,5% en masse de glycérol. Les conditions opératoires de cette réaction entraînent des modifications structurales et texturales des catalyseurs. Cependant, le support TiO2 est identifié comme étant celui conduisant à la meilleure stabilité de la phase métallique dans les conditions de réaction. Une plus grande acidité (de Lewis et de Brønsted) est obtenue sur les catalyseurs supportés sur alumine-silice. Pendant la transformation du glycérol, les sites acides sont impliqués dans les réactions de déshydratation sélectivement recherchées, mais peuvent promouvoir les ruptures indésirables de liaisons C-C par un mécanisme de craquage acide. La production d'alcanes s'avère relativement faible pour tous les catalyseurs testés. Les catalyseurs au Ru montrent une forte activité, mais avec une sélectivité importante en CH4. Les ajouts d'étain permettent de diminuer légèrement la formation de ce produit de dégradation indésirable. Parmi tous les catalyseurs au Pt, ceux supportés sur TiO2 montrent les meilleures conversions du glycérol et les meilleures sélectivités en produits C3 valorisable / The selective hydrogenolysis of glycerol to C3 compounds (propanediol, propanol, propane) was studied in aqueous phase on bifunctionnal catalysts composed of ruthenium, alone or modified by Sn additions, or of platinum supported on alumina, alumina-silica or titania. Tin was added by various methods: co-impregnation, successive impregnation and catalytic reduction.The glycerol hydrogenolysis was performed in batch reactor, at 210°C, 60 bar of total pressure (under N2 or H2), 4.5 wt% glycerol aqueous solution. These operating conditions involve structural and textural modifications of the catalysts. However, the TiO2 support is identified as leading to the best stability of the metallic phase in the reaction conditions. A higher acidity (Lewis and Brønsted sites) is obtained on catalysts supported on alumina-silica. During the transformation of glycerol, the acid sites are implied in the selectively intended dehydration reactions, but can promote the undesirable C-C bond cleavages by a mechanism of acid cracking. The selectivity to alkanes remains relatively low for all the tested catalysts. Ru based catalysts show a high activity with an important selectivity to CH4. Adding of tin allows to slightly decrease the selectivity to this degradation product. Among all the Pt-based catalysts, those supported on TiO2 show the best conversions of glycerol and the best selectivity to C3 valuable products.