Rozprawy doktorskie na temat „Olefin oxidation”

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2014.
Cataloged from PDF version of thesis. Vita.
Includes bibliographical references.
Chapter 1 describes work toward solid-supported W olefin metathesis catalysts. Attempts to tether derivatives of the known Z-selective catalyst W(NAr)(C₃H₆)(pyr)(OHIPT) (Ar = 2,6- diisopropylphenyl, pyr = pyrrolide; HIPT = 2,6-bis-(2,4,6-triisopropylphenyl)phenyl) to a modified silica surface by covalent linkages are unsuccessful due to destructive interactions between W precursors and silica. W(NAr)(C₃H₆)(pyr)(OHIPT) and W(NAr)(CHCMe₂Ph)(pyr)(OHIPT-NMe₂) (HIPT-NMe 2 = 2,6-bis-(2,4,6-triisopropylphenyl)-4- dimethylaminophenyl) are adsorbed onto calcined alumina. W(NAr)(C 3H6 )(pyr)(OHIPT) is destroyed upon binding to alumina, while W(NAr)(CHCMe 2Ph)(pyr)(OHIPT-NMe 2) appears to bind through a non-destructive interaction between the dimethylamino group and an acidic surface site. The heterogeneous catalysts perform non-stereoselective metathesis of terminal olefins, and W(NAr)(CHCMe₂Ph)(pyr)(OHIPT-NMe₂) can be washed off the surface with polar solvent and perform solution-phase Z-selective metathesis. Chapter 2 details selective metathesis homocoupling of 1,3-dienes with Mo and W monoalkoxide pyrrolide (MAP) catalysts. A catalytically relevant vinylalkylidene complex, Mo(NAr)(CHCHCH(CH₃)₂)(Me₂pyr)(OHMT) (HMT = 2,6-bis(2,4,6-trimethylphenyl)phenyl; Me₂pyr = 2,5-dimethylpyrrolide), is isolated. A series of Mo and W MAP catalysts is synthesized and tested for activity, stereoselectivity, and chemoselectivity in 1,3-diene metathesis homocoupling. Catalysts containing the OHIPT ligand display excellent selectivity in general, and W catalysts are less active but more selective than their Mo counterparts. Chapter 3 recounts the synthesis and characterization of several heteroatom-substituted alkylidene complexes with the formula Mo(NAr)(CHER)(Me₂pyr)(OTPP) (TPP = 2,3,5,6- tetraphenylphenyl; ER = OPr, N-pyrrolidinonyl, N-carbazolyl, pinacolborato, trimethylsilyl, SPh, or PPh2). Synthesis proceeds via alkylidene exchange between Mo(NAr)(CHR)(Me₂pyr)(OTPP) (R = H, CMe₂Ph) and a CH₂CHER precursor. Each complex behaves similarly to known MAP complexes in olefin metathesis processes; the electronic identity of ER has little effect on catalytic properties. Distinctive features of alkylidene isomerism and catalyst resting state are examined. Chapter 4 contains synthetic and catalytic studies of thiolate-containing Mo and W imido alkylidene complexes. The species M(NAr)(CHCMe 2Ph)(pyr)(SHMT) (M = Mo or W), Mo(NAr)(CHCMe₂Ph)(Me₂pyr)(STPP), and Mo(NAr)(CHCMe₂Ph)(STPP)₂ are synthesized by substitution of the appropriate thiol or thiolate ligands for pyrrolide or triflate ligands in metal precursors. These complexes show similar structural and spectral characteristics to alkoxidecontaining species. The thiolate complexes and their alkoxide analogues are compared for activity and selectivity in metathesis homocoupling and ring-opening metathesis polymerization processes. In general, thiolate catalysts are slower and less selective than alkoxide catalysts.
by Erik Matthew Townsend.
Ph. D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012.
Vita. Cataloged from PDF version of thesis.
Includes bibliographical references.
Chapter 1: Reaction of W(CCMe3)Cl 3(dme) with one equivalent of (3,5-Me 2C6H3NCH2CH 2)3N)Li3 affords yellow, crystalline W(CCMe3)(N3N) in good yield. The reactivity of this new alkylidyne complex towards terminal alkynes was investigated. Two other new tungsten alkylidynes, W(CCMe3)(pyr) 3 (pyr = 2,5-dimethylpyrrolide) and W(CCMe3)(Ph 2N)3 were prepared by the addition of three equivalents of lithium dimethylpyrrolide or lithium diphenylamide, respectively, to W(CCMe3)Cl 3(dme). The reactivity of these new alkylidynes with various alcohols is reported. The reactivity of several tungsten alkylidyne compounds towards ligand displacement by surface silanols is reported, resulting in the synthesis of several new silicasupported tungsten alkylidynes. The alkyne metathesis activity of all new homogeneous and heterogeneous alkylidyne complexes is reported. Chapter 2: Addition of one equivalent of 2,4,6,2',4',6'-hexaisopropylterphenol to Mo(NAd)(CHCMe 2Ph)(pyr)2 results in the formation of Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (HIPTO = hexaisopropylterphenoxide). This new alkylidene compound was found to catalyze the metathesis of 1-hexene in 20% yield to 95% cis 5-decene, which represents the first report of highly Z-selective metathesis homocoupling of a terminal olefin. The decomposition of the catalyst in the presence of ethylene is explored. The syntheses of several new bulky achiral phenoxide ligands are presented, along with the syntheses of the corresponding MAP (monoalkoxide monopyrrolide) molybdenum imido alkylidene compounds. The reactivity of new MAP compounds containing bulky phenoxide ligands towards the Z-selective metathesis of terminal and internal olefins is presented. The cis-selectivity of this system is proposed to arise from the combination of a relatively small imido ligand in conjunction with a very bulky alkoxide forcing the substituents of the substrate to point in this same direction with each insertion. Photolysis of MAP compounds with 366 nm radiation was found to produce significant amounts of anti alkylidenes, and the kinetics of decay of unstable anti alkylidenes are investigated. Chapter 3: The reaction of 2,3-dicarbomethoxynorbomadiene (DCMNBD) with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) (Ad = 1-adamantyl, HIPTO = hexaisopropylterphenoxide) affords >98% cis, >98% tactic polyDCMNBD. The tacticity of this polymer is proved to be syndiotactic through polymerization of DCMenthNBD (2,3-dicarbomenthoxynorbomadiene) and IH- H COSY. A variety of related MAP alkylidene compounds are also investigated towards the ROMP of DCMNBD and found to produce polyDCMNBD in a range of tacticities and cis contents. Highly cis polyNBDF6 (poly-bis(CF 3)-norbomadiene) was also prepared using molybdenum MAP compounds, and the resulting polymer was found to be essentially insoluble in common organic solvents. Solid state CPMAS 13C NMR spectroscopy revealed insoluble polyNBDF6 to be highly tactic, and the tacticity is proposed to be syndiotactic. Cis, tactic polymer was prepared through the addition of 3,3-methylphenylcyclopropene (MPCP) to molybdenum MAP compounds. Attempts towards determination of the tacticity of cispolyMPCP are presented, including the synthesis of three 3,3-disubstituted cyclopropene monomers containing chiral tags. The cis-selective ROMP of cyclooctene and 1,5- cyclooctadiene are reported. The syndioselectivity of the catalysts is proposed to be controlled by the configuration of the 4-coordinate metal center, which alternates with each insertion of monomer. Chapter 4: Racemic 2,3-dicarbomethoxynorbornene (rac-DCMNBE) is polymerized by Mo(NAd)(CHCMe 2Ph)(pyr)(HMTO) (Ad = 1-adamantyl, pyr = pyrrolide, HMTO = hexamethylterphenoxide) to afford an all-cis polymer that is syndiotactic and composed of alternating enantiomers. The cis, syndiotactic ROMP of several other racemic chiral monomers are reported, also affording structures containing a high degree of enantiomer alteration. Attempts towards the alternating copolymerization of two different monomers are reported. The ROMP of enantiomerically pure (+)-dicarbomethoxynorbornene with Mo(NAd)(CHCMe 2Ph)(pyr)(HIPTO) leads to the production of 92% trans-isotactic polyDCMNBE. The structure of trans-isotactic polyDCMNBD is proved through hydrogenation and comparison of its 3C NMR spectrum with that of known cis-isotactic polyDCMNBE. Both cis/syndiotactic/alternating poly-rac-DCMNBE and trans/isotactic poly-(+)-DCMNBE are polymer structures that have not been previously reported. The thermal properties of all new polymers and their hydrogenated counterparts are reported and are found to correlate closely with polymer structure.
by Margaret McGuigan Flook.
Ph.D.

The study and the development of innovative metal-catalysed systems for the oxygenation of organic molecules with sustainable oxidants, and especially molecular oxygen, O2, or hydrogen peroxide, H2O2, is a very attractive perspective for the Chemical Industry. In the Thesis project, different strategies have been addressed to implement benchmark oxidative transformations, including the autooxidation of benzylic derivatives, the hydroxylation of aromatic hydrocarbons and the epoxidation of olefins. In all cases, the research approach has been based on some key issues, namely the integrated use of: i) bulk oxidants with low environmental impact, such as O2 and H2O2; ii) multi-metallic catalysts with thermal, hydrolytic and oxidative resistance, tailored functionality and solubility; iii) heterogeneous catalysis techniques with membrane-based hybrid organic-inorganic functional materials and solvent-free protocols; iv) microwave irradiation and/or photoirradiation as non-conventional activation techniques, v) multiple catalysis techniques, with sequential and/or parallel processes (Concurrent Tandem Catalysis). The choice of the catalyst package has been established within the class of molecular polyanionic metals oxides clusters, known as polyoxometalates (POMs), with general formula [XxMmOy]q-, where M is the main metallic component (Mo, V, W) and X is an eventual heteroatom such as P or Si. These complexes offer a unique opportunity because of their prevalent inorganic, robust nature, and high versatility in terms of structure, chemical composition, electron density and polyanionic charge. Moreover, a rewarding approach has been recently devised for the catalyst upgrade, by decorating the POM scaffold with organic domains, yielding hybrid organic-inorganic catalysts with superior performances. Since fluorinated phases are of particular interest for performing oxidative transformations, the research activity has been focused on the synthesis, characterization and catalytic activity of novel fluorous-tagged polyoxometalates. Two diverse synthetic approaches have been adopted, based on counterion metathesis and on the covalent functionalization of the POM inorganic surface. With the first strategy, the decatungstate polyanion (W10O32)4- has been isolated in the presence of a fluorous-tagged tetraalkylammonium cation, yielding the fluorophilic salt ?[CF3(CF2)7(CH2)3]3CH3N}4W10O32 , (RfN4W10). Decatungstate is known to be an efficient initiator of autooxidation pathways under photoirradiation, in a oxygen atmosphere. Therefore, the photocatalyzed oxidation of benzylic hydrocarbons, including ethylbenzene and cumene, by RfN4W10 and O2, has been performed in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), both in homogeneous and heterogeneous conditions. The application of membrane technology for the heterogeneous catalysis, in particular, offers the combination of advanced molecular separation and selective transport properties, with the reactivity on a solid support. The photocatalyst heterogenisation has thus been obtained by incorporation of RfN4W10 in perfluorinated polymeric films of HYFLON AD 60X, thus providing novel hybrid materials to be employed and recycled in multi-turnover processes, in solvent-free conditions. Scanning electron microscopy (SEM) images of the film surface and cross-section highlight a highly dispersed, homogeneous distribution of the catalyst domains which appear as spherical particles with uniform size of approximately 2-3 ?m in diameter. Furthermore, in particular conditions, a porous membrane has been obtained, allowing the use of a continuous flow reactor. In the conditions explored, the photooxygenation by (RfN)4W10O32 yields the benzylic hydroperoxide and the corresponding alcohol and ketone. Noteworthy, tetraline and indane photooxygenation proceeds with TON>6000 and remarkable alcohol selectivity, thus providing a convenient alternative to other radical-centered oxygenation systems. Fluorous-tagged polyoxometalates have also been synthesised through a covalent functionalization approach. This alternative strategy employs vacant polyoxotungstates and the fluorinated organosilyl chloride CF3(CF2)7CH2CH2SiCl3 (RfSiCl3) to afford hybrid derivatives through the covalent attachment of the organic groups on the POM surface. The resulting complexes, with general formula Q4[(RfSi)xOySiWwOz], isolated as tetrabutylammonium (Q+) salts, have been characterised and used as catalysts for the epoxidation of different olefins in the presence of H2O2. Kinetic and mechanistic studies have provided several insights on the synergistic effect between the catalysts and the fluorinated solvent used, the hexafluoro-isopropanol (HFIP). Noteworthy, under microwave irradiation, the epoxide is produced with quantitative yield and only after 20 minutes, even for terminal olefins. A further aspect concerns the self-assembly of the POM-based fluorous-tagged amphiphiles. Aggregation phenomena in HFIP solution have been studied by DLS and monitored in the solid state by electronic microscopy. The upgrade to heterogeneous catalysis has also been achieved through the covalent functionalization approach. In this case, the vacant polyoxotungstate has been reacted with the organo silyl chloride CH2=CH(CH2)6SiCl3 (RSiCl3), bearing a terminal alkene residues. The morphology and structure of the resulting hybrid materials have been tuned upon variation of comonomers and porogenic solvents ratio. Interestingly, the hybrid polymer swells in fluorinated alcohols, where the epoxidation of cis-cyclooctene, occurs with quantitative yield after 15 min. Finally, POM-based catalysis has also been applied to the synthesis of phenol which is one of the most valuable intermediate and commodity chemical on the market. To this aim the research activity has been focussed on the implementing both the autoxidation pathway, and the direct mono-hydroxylation of benzene. (i) The application of Tandem Catalysis techniques, so to exploit the membrane-based photocatalytic production of the cumene hydroperoxide and foster its decomposition to phenol through a second step by a acid POM catalyst; (ii) the screening of several molybdovanadate catalyst to be used with H2O2 for benzene hydroxylation. In the first case, the POM mediated tandem catalysis yields 63% phenol with respect to the initial amount of cumyl-hydroperoxide.; in the second case, with the vanadium mono-substituted undecamolybdate, H4Mo11VO40, an improvement of literature results has been obtained through reaction optimization, thus giving: 17 % conversion of benzene at 50°C in CH3CN, with selectivity = 90 % and TOF = 22.5 h-1.
Lo studio e lo sviluppo di sistemi metallo-catalizzati innovativi per l’ossidazione di molecole organiche con ossidanti sostenibili, specialmente ossigeno molecolare, O2, o acqua ossigenata, H2O2, è una prospettiva di grande attrazione per l’Industria Chimica. Nel progetto di Tesi di Dottorato, sono state sviluppate diverse strategie allo scopo di effettuare trasformazioni ossidative di riferimento quali l’autoossidazione di derivati benzilici, l’idrossilazione di idrocarburi aromatici e l’epossidazione di olefine. In tutti i casi, l’approccio alla ricerca si è basato su alcuni aspetti chiave che prevedono l’utilizzo integrato di: i) ossidanti a basso impatto ambientale quali O2 e H2O2; ii) catalizzatori multi-metallici ad elevata resistenza termica, idrolitica ed ossidativa; iii) tecniche di catalisi eterogenea per mezzo di materiali funzionali ibridi organici-inorganici costituiti da membrane catalitiche a matrice polimerica e protocolli che non prevedano l’impiego di solventi organici; iv) microonde o radiazioni fotochimiche quali tecniche di attivazione non convenzionali; v) tecniche di catalisi multipla con processi sequenziali e/o paralleli (Tandem Catalisi). I catalizzatori impiegati appartengono alla classe degli ossidi polianionici metallici, detti poliossometallati (POMs), aventi formula generale [XxMmOy]q-, dove M è il componente metallico principale (Mo, V, W) e X è un eventuale eteroatomo (P o Si). Questi complessi sono molto vantaggiosi come catalizzatori perché di natura inorganica, resistenti e sono modulabili in termini di struttura, composizione chimica, densità elettronica e carica polianionica. Particolarmente interessante è la possibilità di funzionalizzare la porzione inorganica con domìni di natura organica, potendo così ottenere catalizzatori ibridi organici-inorganici dalle prestazioni catalitiche migliori. Poiché le fasi fluorurate sono di particolare interesse per ciò che concerne le trasformazioni ossidative, l’attività di ricerca si è focalizzata sulla sintesi, caratterizzazione e attività catalitica di nuovi poliossometallati fluorurati. Sono state seguite due strategie di sintesi differenti basate sulla metatesi di controcatione e sulla funzionalizzazione covalente di superfici di POM inorganici. Con la prima strategia è stato isolato il polianione decatungstato (W10O32)4- con un controcatione tetraalchilammonio fluorurato ottenedo il sale fluorofilico ?[CF3(CF2)7(CH2)3]3CH3N}4W10O32 , (RfN4W10). Il decatungstato è noto per la sua capacità di essere iniziatore di processi radicalici se fotoirradiato in atmosfera di ossigeno. L’ossidazione fotocatalitica di etilbenzene ed altri idrocarburi benzilici tramite RfN4W10 e O2 è stata condotta in 1,1,1,3,3,3-hexafluoroisopropanolo (HFIP), sia in omogeneo che in fase eterogenea. L’applicazione della tecnologia delle membrane per la catalisi eterogenea offre, in particolare, numerosi vantaggi in termini di combinazioni di avanzati processi di separazione molecolare con proprietà di trasporto selettive, insieme alla reattività su supporti solidi. L’eterogeneizzazione del fotocatalizzatore è stata così ottenuta per incorporazione di RfN4W10 in film polimerici perfluorurati di HYFLON AD 60X, ottenendo così nuovi materiali ibridi da impiegare e reciclare in processi “multi-turnover” ed in assenza di solventi. Immagini di microscopia elettronica a scansione (SEM) della superficie e della sezione del film evidenziano una distribuzione omogenea ed altamente dispersa dei domini catalitici che appaiono come particelle sferiche a dimensioni uniformi e di diametro pari a circa 2-3 ?m. Inoltre, in condizioni controllate, è stato possibile ottenere una membrana porosa da poter utilizzare in un reattore a flusso continuo. Nelle condizioni testate, la fotoossigenazione con (RfN)4W10O32 dà benzilidroperossido ed il corrispondente alcool e chetone. E’importante evidenziare come la fotoossigenazione di tetralina ed indano proceda con TON>6000 e con una elevata selettività in alcool, fornendo così un’ importante alternativa ad altri sistemi di ossigenazione basati su meccanismi di tipo radicalico. Poliossometallati fluorurati sono stati sintetizzati anche tramite l’approccio di funzionalizzazione covalente. Questa strategia prevede l’impiego di poliossotungstati lacunari e organosilil cloruri CF3(CF2)7CH2CH2SiCl3 (RfSiCl3) a dare derivati ibridi per mezzo dell’attacco covalente dei gruppi organici sulla superficie del POM. I complessi finali risultanti, con formula generale Q4[(RfSi)xOySiWwOz], isolati come sali di tetrabutilammonio (Q+) sono stati caratterizzati ed impiegati come catalizzatori per l’epossidazione di diverse olefine in presenza di H2O2. Studi cinetici e meccanicistici hanno fornito diverse indicazioni circa l’esistenza di un effetto sinergico fra i catalizzatori e il solvente per fluorurato utilizzato (HFIP). E’importante sottolineare come questa reazione attivata da microonde produca epossido in rese quantitative dopo soli 20 minuti anche per le olefine terminali. Ulteriori aspetti trattati riguardano le caratteristiche auto-assemblanti di questi complessi fluorurati anfifilici. Fenomeni di aggregazione in soluzione di HFIP sono stati studiati tramite DLS e tramite microscopia elettronica allo stato solido. Anche l’eterogeneizzazione di questo sistema è stata ottenuta tramite l’approccio di funzionalizzazione covalente. In questo caso, il poliossotungstato lacunare è stato fatto reagire con un silano che porta una catena alchilica insatura terminale: CH2=CH(CH2)6SiCl3 (RSiCl3). La morfologia e la struttura del materiale ibrido risultante sono state modulate attraverso la variazione del rapporto dei solventi porogenici e dei comonomeri impiegati nella miscela di polimerizzazione. Il polimero ibrido finale presenta l’interessante proprietà di rigonfiare in alcool fluorurati, dove l’epossidazione di cis-cicloottene avviene con rese quantitative in 15 minuti. Infine, è stato studiato il processo POM-catalizzato per la sintesi di fenolo: uno degli intermedi e commodity a più alto valore di mercato. A questo scopo l’attività di ricerca è stata incentrata sullo studio sia del processo autoossidativo, sia della mono-idrossilazione diretta del benzene. (i) L’applicazione di tecniche di Tandem Catalisi, allo scopo di sfruttare la produzione con sistema a membrana foto catalitica del cumilidroperossido da cumene, e promuoverne la sua decomposizione a fenolo in un secondo stadio con un catalizzatore POM-acido, (ii) lo screening di diversi molibdovanadati come catalizzatori da usare con H2O2 per l’idrossilazione di benzene. Nel primo caso, la Tandem Catalisi permette di ottenere una resa in fenolo pari a 63% rispetto alle moli iniziali di cumilidroperossido, nel secondo caso, con H4Mo11VO40 si ha un miglioramento dei dati di letteratura per ottimizzazione della reazione con 17% di conversione, selettività = 90% e TOF = 22.5 h-1.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2015.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Chapter 1 details the synthesis of tungsten imidoalkylidene compounds bearing strongly electron-withdrawing imido ligands. An alternative synthesis involving the treatment of WCl6 with 4 equivalents of N-trimethylsilyl-substituted anilines and subsequent workup with 1,2-dimethoxyethane (DME) has been employed to form complexes of the type W(NAr)2C12(dme); syntheses employing WO2C 2(dme) as the tungsten precursor were unsuccessful. Alkylation with neopentylmagnesium chloride (ClMgNp) and subsequent treatment with trifluoromethanesulfonic acid (HOTf) affords imidoalkylidene species W(NAr)(CHCMe 3)(OTf)2(dme) (OTf = trifluoromethanesulfonate); analogous neophylidene ([W]CHCMe 2Ph) species could not be made under these conditions. Treatment of these compounds with two equivalents of LiO(2,6-(CHCPh 2)C6H3)-Et2O affords the bisaryloxide complexes of the type W(NAr)(CHCMe3)(OR)2. Ring-Opening Metathesis Polymerization (ROMP) studies using a series of these bisaryloxides show that rates of ROMP increase as the electron-withdrawing power of the substituents on the imido ligand increase if steric bulk about the metal center is held constant. A similar trend between two bisaryloxides is observed for anti-to-syn alkylidene rotation rates at 50*C in toluene-d8 . Difficulties synthesizing bis-pyrrolide complexes of the type W(NAr)(CHCMe3)(pyr)2 precluded their use as catalyst precursors; some MAP species containing the more sterically encumbering 2,5-dimethylpyrrolide ligand are presented and the metathesis activity of MAP species bearing the 2,5-dimethylpyrrolide ligand is discussed. Chapter 2 introduces Mo and W complexes bearing the current extreme in sterically bulky imido ligands, the NHIPT (HIPT = 2,6-(2,4,6-iPr 3CH2)CH3) ligand, in an effort to generate all anti alkylidene species. A non-traditional synthetic route is employed in order to install this ligand first as an anilide, and after subsequent proton transfer, as an imido ligand to form a mixed imido species of the type M(NHIPT)(N'Bu)(NH'Bu)Cl. Addition of one equivalent of 2,6-lutidinium chloride, followed by alkylation affords dialkyl species M(NHIPT)(N'Bu)Np 2, and treatment with three equivalents of pyridinium chloride yields all anti imidoalkylidene dichloride species as mono-pyridine adducts, M(NHIPT)(CHCMe 3)C 2(py) (M = Mo, W). General reactivity, including strategies for removal of the pyridine adduct as well as substitution and metathesis chemistry, are discussed. ROMP of MPCP (MPCP = 3-methyl-3-phenylcyclopropene) by a Mo-based MAP species bearing the NHIPT ligand yields predominantly cis,syndiotactic poly(MPCP) and in the homo-metathesis of 1 -octene yields ~81% cis-7-tetradecene. The possible source of trans olefinic product is addressed. Chapter 3 presents the synthesis of the first (1-adamantyl)imido species of tungsten. The functional equivalent of common bisimido precursors for other Mo/W alkylidene species, [W(NAd) 2C 2(AdNH2)1 2, is shown to be a dimer stabilized by hydrogen-bonding interactions between adamantylamine protons and adjacent chlorides bound to the second metal of the dimer. Subsequent alkylation with ClMgNp affords the expected dialkyl species, and treatment with three equivalents of 3,5-lutidinium chloride affords imidoalkylidene complex W(NAd)(CHCMe 3)(C) 2(lut)2 (lut = 3,5-dimethylpyridine). The most desirable synthetic route toward monoalkoxide pyrrolide (MAP) species proceeds through a monoaryloxide monochloride intermediate W(NAd)(CHCMe 3)(Cl)(OAr)(lut) (Ar = 2,6-(2,4,6-Me 3)C6H3, 2,6-(2,4,6-'Pr 3)C6H3). Removal of lutidine with B(C6 F5 )3 and subsequent treatment with lithium pyrrolide affords W(NAd)(CHCMe3)(pyr)(OAr) (pyr = pyrrolide); 2,5-dimethylpyrrolide analogues (W(NAd)(CHCMe3)(Me2pyr)(OAr) can be accessed via protonolysis by HOAr from W(NAd)(CHCMe3)(Me2pyr)2(lut).
by Jonathan Clayton Axtell.
Ph. D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2004.
Vita.
Includes bibliographical references.
Enantiomerically pure molybdenum imido alkylidene complexes of the type Mo(NAr)(CHCMe₂Ph)[Ar'](THF), which contained 3,3'-diaryl (Ar' = Mes (21), Ph (22)) substituted binaphtholate ligands, were prepared and structurally characterized. Complex 21 was a trigonal bipyramidal anti alkylidene complex; both 21 and 22 were anti-THF adducts. Temperature and concentration dependent enantioselective desymmetrization of prochiral trienes by catalyst 21 afforded five- and six-membered heterocycles in >90% conversion and >90% ee. Consumption of the six-membered substrate followed pseudo first-order kinetics. The new catalyst was compatible with a variety of common functional groups. The longevity of the catalysts depended on the concentration of ethylene in solution. The resting state of the catalytic cycle, unsubstituted molybdacyclobutane 70, slowly decomposed to yield propylene. This observation suggests that β-hydride elimination can compete with bimolecular coupling of methylene complexes under some conditions. Chapter 2: Racemic and enantiomerically pure tungsten imido alkylidene complexes, W(NAr)-(CHCMe₂Ph)(Biphen) (23a, Ar = 2,6-i-Pr₂C₆H₃) and W(NAr')(CHCMe₂Ph)(Biphen) (23b, Ar' = 2,6-Me₂C₆H₃) were prepared and shown to be viable catalysts for representative asymmetric ring- closing metathesis reactions. Both catalysts were compatible with a variety of common functional groups. Intermediate tungstacyclobutane complexes were observed when a stoichiometric amount of desymmetrization substrate 62 was added to 23a. The final stable complex 78, formed between the ring-closed product and a tungsten methylene complex, was structurally characterized. Isotopic labeling experiments with ¹³C₂H₄ allowed the observation of
(cont.) unsubstituted tungstacyclobutane complexes (82), ethylene complexes (84), tungstacyclopentane complexes (86), and a heterochiral methylene dimer (85a). The tungstacyclopentane complexes catalyzed slow dimerization of ethylene to 1-butene. The observation of the methylene dimer provides the first direct evidence of a bimolecular decomposition pathway for methylene complexes. Chapter 3 Racemic and enantiomerically pure molybdenum alkylimido alkylidene complexes, Mo(NAd)(CHCMe₂Ph)(Biphen) (19d, Ad = 1-adamantyl) and Mo(NAd)(CHCMe₂Ph)[Trip]-(THF) (20d) were prepared and structurally characterized. Complex 19d was observed almost exclusively as a syn alkylidene isomer, in contrast with 20d which was observed almost exclusively as an anti-THF adduct. Complexes 19d and 20d are the only reported chiral alkylimido alkylidene complexes for enantioselective olefin metathesis reactions. Complex 19d is the first crystallographically characterized four-coordinate adamantylimido alkylidene complex in its base-free form. It offers unique reactivity and selectivity profiles in tandem AROM/RCM and AROM/CM reactions. Complex 19d is compatible with a variety of common functional groups, including boron-containing reagents. Van't Hoff analyses suggest that the bias toward syn-19d isomer is entropy-driven. Chapter 4: Solvent- and base-free molybdenum methylene complexes, Mo(NAr)(Biphen)(CH₂) (114a, Ar = 2,6-i-Pr₂C₆H₃) and Mo(NAd)(Biphen)(CH₂) (114d, Ad = 1-adamantyl) ...
by W.C. Peter Tsang.
Ph.D.

The oxidation of alcohols and olefins is a pivotal reaction in organic synthesis. However, traditional oxidants are toxic and they often release a considerable amounts of by-products. Here, two IronIII-based systems are shown as oxidative catalyst, working in mild conditions with hydrogen peroxide as primary oxidant. An efficient catalytic system for the selective oxidation of several alcohols to their corresponding aldehydes and ketones was developed and characterized, [Fe(phen)2Cl2]NO3 (phen=1,10-Phenantroline). It was demonstrated that the adoption of a buffered aqueous solution is of crucial importance to ensure both considerable activity and selectivity.The Iron - Thymine-1-acetic acid in-situ complex was studied as catalyst in alcohol oxidations and C-H oxidative functionalization, involving hydrogen peroxide as primary oxidant in mild reaction conditions. The catalytic ability in alcohol oxidations was investigated by Density Functional Theory calculations, however the catalyst still has uncertain structure. The system shows satisfactory activity in alcohol oxidation and aliphatic rings functionalization. The Fe-THA system was studied in cyclohexene oxidation and oxidative halogenations. Halide salts such as NBu4X and NH4X were introduced in the catalytic system as halogens source to obtain cyclohexene derivatives such as halohydrins, important synthetic intermediates.The purpose of this dissertation is to contribute in testing new catalytic systems for alcohol oxidations and C-H functionalization. In particular, most of the efforts in this work focus on studying the Iron - Thymine-1-acetic acid (THA) systems as non-heme oxidative model, which present: •an iron metal centre(s) as a coordinative active site, •hydrogen peroxide as a primary oxidant, •THA as an eco-friendly, biocompatible, low cost coordinating ligand.

Polymer functional groups have critical impacts upon physical, chemical and mechanical properties, and thus affect the specific applications of the polymer. Functionalization of cellulose esters and ethers has been under extensive investigation for applications including drug delivery, cosmetics, food ingredients, and automobile coating. In oral delivery of poorly water-soluble drugs, amorphous solid dispersion (ASD) formulations have been used, prepared by forming miscible blends of polymers and drugs to inhibit crystallization and enhance bioavailability of the drug. The Edgar and Taylor groups have revealed that some cellulose omega-carboxyalkanoates were highly effective as ASD polymers, with the pendant carboxylic acid groups providing both specific polymer-drug interactions and pH-triggered release through swelling of the ionized polymer matrix. While a variety of functional groups such as hydroxyl and amide groups are also of interest, cellulose functionalization has relied heavily on classical methods such as esterification and etherification for appending functional groups. These methods, although they have been very useful, are limited in two respects. First, they typically employ harsh reaction conditions. Secondly, each synthetic pathway is only applicable for one or a narrow group of functionalities due to restrictions imposed by the required reaction conditions. To this end, there is a great impetus to identify novel reactions in cellulose modification that are mild, efficient and ideally modular. In the initial effort to design and synthesize cellulose esters for oral drug delivery, we developed several new methods in cellulose functionalization, which can overcome drawbacks of conventional synthetic pathways, provide novel cellulose derivatives that are otherwise inaccessible, and present a platform for structure-property relationship study. Cellulose omega-hydroxyalkanoates were previously difficult to access as the hydroxyl groups, if not protected, react with carboxylic acid/carbonyl during a typical esterification reaction or ring opening of lactones, producing cellulose-g-polyester and homopolyester. We demonstrated the viability of chemoselective olefin hydroboration-oxidation in the synthesis of cellulose omega]-hydroxyesters in the presence of ester groups. Cellulose esters with terminally olefinic side chains were transformed to the target products by two-step, one-pot hydroboration-oxidation reactions, using 9-borabicyclo[3.3.1]nonane (9-BBN) as hydroboration agent, followed by oxidizing the organoborane intermediate to a primary alcohol using mildly alkaline H2O2. The use of 9-BBN as hydroboration agent and sodium acetate as base catalyst in oxidation successfully avoided cleavage of ester linkages by borane reduction and base catalyzed hydrolysis. With the impetus of modular and efficient synthesis, we introduced olefin cross-metathesis (CM) in polysaccharide functionalization. Using Grubbs type catalyst, cellulose esters with terminally olefinic side chains were reacted with various CM partners including acrylic acid, acrylates and acrylamides to afford families of functionalized cellulose esters. Molar excesses of CM partners were used in order to suppress potential crosslinking caused by self-metathesis between terminally olefinic side chains. Amide CM partners can chelate with the ruthenium catalyst and cause low conversions in conventional solvents such as THF. While the inherent reactivity toward CM and tendency of acrylamides to chelate Ru is influenced by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides. We observed that the CM products are prone to crosslinking during storage, and found that the crosslinking is likely caused by free radical abstraction of gamma-hydrogen of the alpha, beta-unsaturation and subsequent recombination. We further demonstrated successful hydrogenation of these alpha, beta-unsaturated acids, esters, and amides, thereby eliminating the potential for radical-induced crosslinking during storage. The alpha, beta-unsaturation on CM products can cause crosslinking due to gamma-H abstraction and recombination if not reduced immediately after reaction. Instead of eliminating the double bond by hydrogenation, we described a method to make use of these reactive conjugated olefins by post-CM thiol-Michael addition. Under amine catalysis, different CM products and thiols were combined and reacted. Using proper thiols and catalyst, complete conversion can be achieved under mild reaction conditions. The combination of the two modular reactions creates versatile access to multi-functionalized cellulose derivatives. Compared with conventional reactions, these reactions enable click or click-like conjugation of functional groups onto cellulose backbone. The modular profile of the reactions enables clean and informative structure-property relationship studies for ASD. These approaches also provide opportunities for the synthesis of chemically and architecturally diverse cellulosic polymers that are otherwise difficult to access, opening doors for many other applications such as antimicrobial, antifouling, in vivo drug delivery, and bioconjugation. We believe that the cellulose functionalization approaches we pioneered can be expanded to the modification of other polysaccharides and polymers, and that these reactions will become useful tools in the toolbox of polymer/polysaccharide chemists.
Ph. D.

Oxidations are an important kind of reactions which are traditionally performed using stoichiometric oxidants that generate a large amount of waste. Syn-dihydroxylation of alkenes is a paradigmatic example because it is a cornerstone reaction in organic synthesis that still relies in the use of heavy metal oxides, specially Os and Ru based oxides in catalytic amounts, but also KMnO4, in stoichiometric amounts. Acetonitrile and halogenated solvents are widely used solvents in these reactions because of their robust nature against oxidants. However, metal catalyzed oxidations in green solvents are basically unknown. Rieske oxygenases are nonheme iron enzymes that catalyzes the olefin cisdihydroxylation among other reactions. Is well know that the FeV(O)(OH) species play a key role as intermediates in arene dihydroxylation catalyzed by Rieske oxygenases. However, the inability to accumulate these intermediates in solution has thus far prevented their spectroscopic and chemical characterization. In this thesis, we were able to synthetizes an iron catalyst bearing a sterically encumbered tetradentate ligand. The steric demand of the ligand was envisioned as a key element to support a high catalytic activity by preventing bimolecular decomposition paths, and facilitating product release. This catalyst provides good to excellent yields of syn-diol products (up to 97% isolated yield) of a broad range of olefins
Les reaccions d’oxidació tradicionalment es realitzen utilitzant oxidants estequiomètrics que generen una gran quantitat de residus. La sin-dihidroxilació d’alquens n’és un exemple paradigmàtic perquè és una reacció que es pot considerar pedra angular en síntesi orgànica, i actualment encara es porta a terme amb oxidants basats en metalls pesats, especialment òxids d’Os i Ru en quantitats catalítiques, però també KMnO4, en quantitats estequiomètriques. L’acetonitril i els dissolvents halogenats són dissolvents àmpliament utilitzats en aquestes reaccions per la seva naturalesa robusta en vers les oxidacions. No obstant això, les oxidacions catalitzades per metalls en dissolvents menys tòxics són bàsicament desconegudes. Les oxigenases de Rieske, són enzims de ferro no hemo que catalitzen la sin-dihidroxilació d’olefines entre altres reaccions. És ben sabut que les espècies de FeV(O)(OH) tenen un paper clau com a intermediaris en la di hidroxilació d’arens catalitzada per les oxigenases de Rieske. No obstant això, la incapacitat per acumular aquests intermedis en solució a impedit, fins ara, la seva caracterització espectroscòpica i química. En aquesta tesi, vam ser capaços de sintetitzar un catalitzador de ferro amb un lligand tetradentat estèticament impedit. La demanda estèrica del lligand es va concebre com un element clau per donar suport a una alta activitat catalítica evitant camins de descomposició bimoleculars i facilitant l’alliberament del producte, proporcionant rendiments entre bons i excel·lents del producte sin-diol (fins a un 97% de rendiment aïllat) per una àmplia gamma d’olefines
Programa de Doctorat en Química

The oxidation of olefins is of central importance in organic synthesis. This thesis is divided into the development of novel approaches to two classes of this transformation: (i) dihydroxylation and (ii) aminohydroxylation. (i) Dihydroxylation 1. Introduction- 1,2-Benzoquinones The chemistry of 1,2-benzoquinones is reviewed, including synthesis and reactivity; particular attention is paid to their cycloaddition chemistry and their reaction as hetero-dienes with alkenes. 2. Results and discussion - Utilising 1,2-benzoquinones as reagents for dihydroxylation The [4+2] reaction of 3,4,5,6-tetrachloro-I,2-benzoquinone as a hetero-diene with a range of alkenes to form the corresponding 2,3-dihydrobenzo[b][1,4]dioxines is studied. The reactivity of a sterically and electronically diverse range of 1,2-benzoquinones with representative alkenes is also studied. The cleavage of a 2,3-dihydrobenzo[b][1,4]dioxine to constitute overall syn-dihydroxylation of the alkene is investigated. (ii) Aminohydroxylation 3. Introduction - Osmium-mediated aminohydroxylation Development of the osmium-mediated aminohydroxylation is discussed, with particular emphasis on its mechanism and the development of an asymmetric variant. The tethered aminohydroxylation (TA) reaction is introduced, including discussion of its scope and limitations. 4. Results and discussion - Development of the osmium-mediated aminohydro~'Ylation reaction Tethered aminohydroxylation Optimisation of the standard TA protocol is investigated. An efficient synthesis of sulfonyloxycarbamate substrates for employment in a novel TA protocol is developed. The scope of the modified reaction is investigated in both allylic and homoallylic systems. Asymmetric aminohydroxylation (AA) The application of sulfonyloxycarbamates and benzoyloxycarbamates in AA reactions is studied, including extensive investigation of reaction conditions. 5. Introduction - MicroscIerodermins Synthetic approaches to the microsclerodermin family of natural products are reviewed. 6. Results and discussion - Towards the synthesis of the microscIerodermins A novel approach to the synthesis of the microsclerodermins utilising the TA reaction is disclosed, including the development of a protecting group strategy based on model studies. 7. Experimental Full experimental procedures and characterisation of compounds are reported.

Perfumery compounds isoeugenol and isosafrole can be oxidized to their aldehydes, vanillin and heliotropin respectively. The aldehydes obtained are very useful and commercially valuable products. Apart from their importance as perfumery compounds, they form important intermediates in the Pharmaceuticals and pesticide industries. Liquid phase oxidation of isosafrole using different oxidizing agents were tried. Sodium dichromate as oxidizing agent in aqueous acetic acid was found to be most suitable because of its higher yields and mild reaction conditions. This reaction was taken up for detailed study. Since the kinetic study of dichromate oxidation in aqueous acetic acid medium of isosafrole has not been mentioned in the literature, various parameters like isosafrole, dichromate and acetic acid concentrations were studied. The experiments were conducted at different temperatures to estimate the activation energy of the reaction. The effect of added salts like manganese sulfate, manganese acetate and cobaltous acetate has also been studied. For all the experiments the change in isosafrole concentration was observed. The rate of reaction increases with increase in isosafrole concentration. The order of the reaction with respect to isosafrole concentration is found to be one. The rate of reaction increases with increase in initial sodium dichromate concentration. The reaction is found to be half order in dichromate ion concentration. The rate of reaction increases with increase in acetic acid concentration with an order two. The atmospheric oxygen does not affect the reaction rate suggests that the reaction may not be free radical reaction. The rate of reaction increases with increase in temperature. The activation energy was found to be equal to 14.59 kcal/mol.

Esta tese apresenta um estudo sobre a contração de anel de olefinas e cetonas cíclicas promovida por sais de tálio(III). A reação de uma série de cicloexanonas e cis e trans-2-decalonas com TTN em CH2Cl2 levou aos correspondentes produtos de contração em rendimentos muito bons, desde que não houvesse um grupo metila em α-carbonila. A reação de 3- e 4-alquilcicloexanonas, bem como de trans-2-decalonas, ocorreu com alto grau de seletividade. As diastereosseletividades observadas estão de acordo com o mecanismo proposto por McKillop. O sistema indânico, resultante da contração de um dos anéis do sistema bicíclico[4.4.0], foi construído de três maneiras diferentes. A reação de 1-tetralonas com TTN/K-10 em pentano forneceu 1-indanocarboxilatos de metila em rendimentos razoáveis, enquanto que o tratamento de 1,2-diidronaftalenos com TTN em MeOH levou aos correspondentes produtos de contração em bons rendimentos, quando não havia grupos alquílicos ligados à dupla ligação. Finalmente, a reação de dois álcoois homoalílicos, contendo a dupla ligação endocíclica, com TTN em uma mistura 1:1 de AcOH e H2O, levou às correspondentes 1-(2,3-diidro-1H-1-indanil)-3-hidroxi-1- propanonas em rendimentos excelentes.
This thesis presents studies toward the ring contraction of ketones and olefins promoted by thallium(III) The reaction of alkylcyclohexanones and cis and trans-2-decalones with TTN in CH2Cl2 led to the corresponding ring contraction products in very good yields, providing there is no methyl group at α-carbonyl position. The reaction of 3- and 4-alkylcyclohexanones, as well as trans-2-decalones, occurred with high degree of selectivity. The observed diastereoselectivities agree with the McKillop\'s mechanism. The indan ring system was constructed by three different protocols. The reaction of 1-tetralones with TTN/K-10 in pentane afforded methyl 1-indanecarboxylates in reasonable yields, while treatment of 1,2-dihydronaphathlenes with TTN in MeOH furnished the corresponding ring contraction products in good yields, as long as there is no alkyl group at the double bond. Finally, the reaction of two homoallylic alcohols, bearing an endocyclic double bond, with TTN in a 1:1 mixture of AcOH and H2O, led to 1-(2,3-dihydro-1H-1-indenyl)-3-hydroxypropan-1-ones in excellent yields.

Les molécules chirales représentent environ 60% des médicaments présents sur le marché pharmaceutique et plus de 80% des médicaments en développement avec plus de 150 milliards de dollars de chiffre d’affaire pour l’année 2002. Les intermédiaires chiraux sont fortement demandés dans l’industrie pharmaceutique atteignant 15 milliards de dollars de chiffre d’affaire en 2009. D’autres domaines en sont demandeurs avec une répartition d’environ 15% dans l’agrochimie et 5% pour la parfumerie. L’obtention de composés d’intérêt pharmaceutique de façon asymétrique est un réel défi et une réelle nécessité. Ces molécules possèdent une architecture spatiale qui entraîne des interactions spécifiques et des affinités particulières avec les enzymes ou des récepteurs biologiques chiraux. L’utilisation de catalyseurs pour accéder à des composés organiques chiraux et plus précisément l’oxydation d’alcanes prochiraux ou d’oléfines constitue un domaine en essor ces dernières décennies. Pour parvenir à synthétiser des molécules chirales, l’industrie pharmaceutique s’est tournée vers l’utilisation de biocatalyseurs en partie pour réaliser différentes réactions stéréo-contrôlées avec la nécessité de séparer les mélanges racémiques par résolution enzymatique. Cependant, les biocatalyseurs présentent un inconvénient majeur qui est généralement le faible rendement en composé chiral recherché et nécessite un savoir faire pour la manipulation de ces enzymes. Les métalloporphyrines sont des catalyseurs comportant un macrocycle tétrapyrrolique et différentes fonctionnalisations en positions méso. Ces molécules ont fait l’objet de nombreuses études qui ont conduit à la synthèse de métalloporphyrines chirales très complexes. Malheureusement, leur synthèse est souvent longue avec de faibles rendements et leur application à un nombre limité de substrats ne permet pas leur généralisation. Ce travail de thèse, développé pour la première fois au laboratoire, s’inscrit dans le cadre d'un contrat CIFRE, dans le but de parvenir à la synthèse de porphyrines chirales facilement accessibles, applicables dans des réactions d’oxydation énantiosélectives efficacement (stabilité). Le premier objectif visé est la synthèse de porphyrines chirales dont la structure ciblée comporte des groupements hétérocycliques azotés chiraux en position méso, reliés par une liaison carbone-hétéroatome (C-N). Nous avons pu atteindre 4 séries de porphyrines qui ont été évaluées dans des réactions d’oxydation énantiosélectives (époxydation, hydroxylation). Le deuxième objectif visé est d’exploiter les propriétés électroniques particulières des porphyrines permettant l’application des porphyrines en tant que photosensibilisant après photoactivation en thérapie anticancéreuse. L’étude des paramètres physiques est primordiale pour déterminer la longueur d’onde d’activation et le rendement quantique. Nous avons souhaité utiliser nos porphyrines et leurs précurseurs en tant qu’agents antiparasitaires, sans photoactivation dans un premier temps, conduisant à la découverte d’activités très intéressantes sur certaines espèce de leishmanies. Enfin, leur application sur P. falciparum nous a permis d’isoler une molécule avec une activité très intéressante. Dans les deux cas, des manipulations avec photoactivation sont en cours
Chiral molecules represent about 60% of drugs in pharmaceutical market and over 80% of drugs in development with more than 150 billion dollars in 2002. Chiral intermediates are in high demand in the pharmaceutical industry producing a turnover of 15 billion dollars in 2009. Other areas are seekers of chiral molecules with a distribution of about 15% in agrochemicals and 5% for the perfume. Asymmetrically production of compounds of pharmaceutical interest is a real challenge. These molecules have a spatial architecture that results in specific interactions and affinity with the enzymes or biological chiral receptors. The use of catalysts to synthesis chiral organic compounds, and more specifically to oxidize alkenes and alkanes having prochiral positions, is a very important area extensively studied in recent decades with few positive results. To achieve the synthesis of chiral molecules, the pharmaceutical industry has turned to the use of biocatalysts, in part, to perform various stereo-controlled reactions with systematically followed by separation of the different isomers by different methodes. However, biocatalysts have a major disadvantage relative to low yields of chiral compound and requires expertise for handling these enzymes. Metalloporphyrins are tetrapyrrolic macrocyle substituted in meso position with various functional groups and incorporating metals (Fe, Mn, Co, Ru). These molecules have been extensively studied and led to the synthesis of many complex chiral metalloporphyrins. Unfortunately, their synthesis is often long with low yields and their application to a limited number of substrates is a major drawback. The first objective of this work is the synthesis of original chiral porphyrins. The targeted structure contains chiral heterocyclic nitrogen groups in two meso positions, connected by a carbon-heteoatom bond (C-N). We were able to reach 4 porphyrins-series that have been evaluated as catalyst in oxidation reactions (epoxidation, hydroxylation). The second objective is to take advantage of specific electronic properties of porphyrins for applications as photosensitizer after photoactivation for cancer by photodynamic therapy. The use of this therapy increased during last decades but poor specificity and solubility of the different porphyrins used in clinic against many cancers prompt us to investigate this area. The study of the physical parameters is essential to determine wavelength activation and quantum yield of a photosensitizer. We wanted to use our porphyrins and their precursors as antiparasitic agents, with and without photoactivation against L. donovani, L. major, T. brucei brucei. Malaria is caused by a protist of the genus of Plasmodium. This parasite has an iron deficiency on one hand and cannot biosynthesize certain amino acids. Strucure analogy of porphyrins with heme led us to evaluate antimalarial activity of several porphyrins against P. falciparum

Bibliography: p. 179-188.
Iron antimony oxide has been known to be an active and selective catalyst for the partial oxidation of propene to acrolein and the oxidative dehydrogenation of 1-butene to 1,3- butadiene. It has become the preferred catalyst for the industrial acrolein formation from propene. The main purpose of this work was to investigate the influence of catalyst parameters such as calcination temperature, Sb:Fe ratio, type of pre-treatment, absence or presence of gaseous oxygen on the activity and selectivity in the partial oxidation of propene. Furthermore the influence of the reaction parameters temperature, space time, partial pressure, time on stream and the carbon chain length of the olefin have been studied in partial oxidation reactions using a fixed bed U-tube glass reactor. Various models have been tested for the rate of formation of products in the range of C₂ to C₆ α-olefins. Increasing the calcination temperature from 500°C to 900°C resulted in an increase of the crystallite diameter and a simultaneous decrease of the surface area which might be ascribed to high temperature sintering of the catalyst. The activity decreased proportional to the decrease of surface area. At the same time the selectivity to acrolein increased with increasing calcination temperature.

ABSTRACT ADDITION OF CARBONYL COMPOUNDS TO THE CYCLIC OLEFINS: SYNTHESIS OF CYCLITOLS Altun, Yasemin M.S., Department of Chemistry Supervisor: Prof. Dr. Metin Balci October 2008, 160 pages Cyclitols have attracted a great deal of attention in recent years owing to biological activities exhibited by them and also their usefulness in the synthesis of other natural products and pharmaceuticals. Carbasugars are also a derivative of cyclitols and they are cyclic monosaccharide analogues which posses &
#8211
CH2OH group in their structure. In this study, novel synthetic strategies leading to cyclitol derivatives were investigated and the synthesis of tetraol (72) and pentaol (73) derivatives containing &
#8211
CH2OH group were achieved successfully. Moreover, by the use of manganese(III) acetate oxidation reactions having considerable synthetic utilities in organic chemistry we developed new synthetic methodologies for the cyclitol derivatives. 1,3- and 1,4-Cyclohexadiene (71 and 10) were synthesized from easily available starting materials in order to be used as key compounds. The use of manganese(III) acetate oxidation reaction provides the creation of &
#8211
CH2OH group and one of the hydroxyl groups and the remaining hydroxyl groups were introduced into the key compounds by the use of singlet oxygen reaction. As a result of this, we had considerable advance in the synthesis of cyclitol derivatives.

La fonctionnalisation sélective de BINOL en position 6 ou 6 et 6' par des groupements 3 - (diméthylamino)prop-1-yn-1-yl est décrite. Cette méthode constitue une stratégie prometteuse pour le développement de nouveaux ligands recyclables. Les complexes de La et Yb correspondants ont été testés dans la réaction d'époxydation des cétones α, β-insaturées. Les complexes d'ytterbium sont les plus efficaces, fournissant les époxydes chiraux attendus avec 90 ou 93% d'excès énantiomérique en conditions homogène et hétérogène, respectivement.Dans le cadre de nos études, nous avons également évalué de nouveaux catalyseurs comportant un ion de manganèse penta-coordinnée [LMn(III)OH]ClO4 et [LMnCl](MnCl4)0,5. Ces complexes ont été testés dans la réaction d'époxydation des oléfines terminales utilisant H2O2/NaHCO3 et PhIO comme oxydant. Il s'avère que le complexe [LMn(III)OH]ClO4 est le catalyseur le plus efficace de la série. Une autre approche également été envisagée : oxyder une molécule d'eau présente dans la sphère de coordination du métal par le Cerium Ammonium Nitrate (CAN) et utiliser l'espèce oxydante ainsi générée pour oxyder des substrats. Nos études ont montré que cette stratégie était possible et permettait d'oxyder des substrats organiques.

Dans cette thèse nous avons eu pour but d’étudier la réactivité des complexes à bas degré d’oxydation du fer stabilisés par des ligands phosphines vis-à-vis des substrats insaturés. Cet objectif s’inscrit dans une démarche plus large d’accès à des systèmes catalytiques au fer capables de transformer de manière sélective l’éthylène, par la réaction d’oligomérisation, vers des alpha-oléfines linéaires courtes (butène-1, héxène-1, octène-1), ce qui n’a jamais été rapporté dans la littérature. Pour se faire, le passage par le mécanisme métallacyclique de transformation de l’éthylène est la voie privilégiée. Cependant, les propriétés électroniques et géométriques de ligand requises pour suivre un tel mécanisme, et en particulier son étape clé de couplage oxydant de deux molécules d’éthylène sur le centre métallique, ne sont pas clairement identifiées. Nous rapportons ici dans un premier temps la synthèse d’une bibliothèque de complexes de fer(II) et fer(III) à base de ligands phosphines présentant des propriétés électroniques et géométriques variées. Ces nouveaux complexes sont opportunément testés en tant que catalyseurs, d’une part pour la réaction d’oligomérisation de l’éthylène; mais également en tant qu’espèces réduites in situ en association avec des diènes (isoprène, butadiène) conduisant à leur polymérisation. Afin de nous rapprocher davantage de notre objectif d’accès aux espèces à bas degré d’oxydation du fer, l’emploi d’une voie de réduction en une étape et en conditions douces est rapportée; conduisant à l’isolement et la caractérisation de neuf complexes phosphorés de fer(0) à 18 et à 16 électrons. Bien qu’a priori inactifs vis-à-vis de l’éthylène ou des oléfines plus longues, nous montrons la capacité de ces complexes à promouvoir des réactions de couplage oxydant de substrats insaturés (alcynes) le couplage catalytique de l’éthylène et du butadiène et l’activation de divers composés tels que les silanes ou les halogénures d’alkyles, posant ainsi un premier jalon vers leur optimisation et application en tant que catalyseurs d’autres réactions, et potentiellement dans l’avenir, pour la transformation de l’éthylène
In this thesis our aim was to study the reactivity of phosphine-based low-valent iron complexes towards unsaturated substrates. This goal is part of a wider approach of access to an iron catalytic system able to transform ethylene in a selective manner, by the reaction of oligomerization, towards short linear alpha-olefins (1-butene, 1-hexene, 1-octene), which is unreported in the literature. To achieve this, going through the metallacyclic mechanism of ethylene transformation is the most likely way. However, the electronic and geometrical features of the ligand required to follow this mechanism, and in particular the key step of the oxidative coupling of two molecules of ethylene to the metal center, are ill-defined. We thus report here in a first part the synthesis of a library of P-based iron(II) and iron(III) complexes bearing varied electronic and geometrical features. These novel complexes are opportunistically screened as catalysts for ethylene oligomerization on one hand, and as in situ reduced species in association with dienes (isoprene, butadiene) leading to the polymerization of the latter substrates, on the other hand. In order to get closer to our goal of access to low-valent iron complexes, the use of a one-pot reduction methodology under mild conditions is reported, leading to the isolation and characterization of nine 18- and 16-electron iron(0) complexes. Even though they do not show reactivity towards ethylene or longer olefins, we demonstrate the ability of these complexes to promote reactions involving the oxidative coupling elementary step of unsaturated substrates (alkynes), the catalytic coupling of ethylene and butadiene and the activation of various compounds such as silanes and organic halides, representing a first milestone towards their optimization and application as catalysts for other reactions, including potentially in the near future, for ethylene transformation

Milk fat composition determines specific rheological, sensory and physicochemical properties of dairy products such as texture, melting point, flavor, color, oxidation rates, and viscosity. Previous studies have shown that milkfats containing higher levels of long chain polyunsaturated fatty acids have lower melting points and decreased solid fat contents which leads to softer-textured products. An increased risk of higher oxidation rates can be a disadvantage of high levels of polyunsaturated fatty acids. Three different milkfat compositions were obtained through dietary manipulation of cows: high oleic content, high linoleic content and control milkfat. Ice cream and butter were processed from the treated and control milks. Butter and ice cream samples then were analyzed to measure differences in fatty acid profiles and firmness. High-oleic and high-linoleic milkfat had lower concentrations of saturated fatty acids, such as C 16:0. Conjugated linoleic acid content was increased in the high-linoleic milkfat. High-oleic milkfat resulted in a softer butter. Ice cream samples were analyzed to measure differences in viscosity, melting point, oxidation rate and sensory perception. Significant differences (P<0.05) were found in the fatty acid profiles of milkfat, ice cream mix viscosity, peroxide values of ice cream after 3 to 5 months of storage, butter color, and butter firmness. Sensory analyses included a scooping test at -18°C to detect differences in texture. A difference test was conducted to determine oxidation flavor differences between the three ice cream treatments at extended storage times. No significant differences were found in the scooping test or the oxidation flavor difference. Manipulation of the cow's diet increased the total amount of unsaturated fatty acids. It also influenced firmness of butter and behavior of peroxide values during extended storage of high-linoleic ice cream.
Master of Science

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES)
A Ag?ncia Nacional de Petr?leo, G?s Natural e Biocombust?veis tem como principal miss?o regulamentar e especificar toda a produ??o e comercializa??o do biodiesel produzido em territ?rio nacional. Para a sua comercializa??o ? necess?rio que o biodiesel passe por um controle r?gido de qualidade, bem como esteja devidamente especificado pelas principais normas. A estabilidade oxidativa que ? um dos par?metros incluso pela norma europ?ia EN 14214 vem adquirindo cada vez mais espa?o em pesquisas por estar intrinsecamente relacionada ? qualidade do biodiesel. Biodiesel ? uma mistura de ?steres alqu?licos de ?cidos graxos obtido, convencionalmente, atrav?s da rea??o de transesterifica??o de um ?leo vegetal ou gordura animal. No entanto, a natureza da mat?ria-prima a qual lhe dar? origem ? um dos fatores determinantes em seu grau de estabilidade, visto que por apresentarem insatura??es em n?mero e em distintas posi??es os tornam suscept?veis ao ataque do oxig?nio atmosf?rico e a condi??es de elevadas temperaturas proporcionando, assim, a sua degrada??o. Uma das principais problem?ticas enfrentadas, atualmente, pela ind?stria de biodiesel prov?m da sua baixa estabilidade levando a uma diminui??o de sua qualidade por longos per?odos de armazenamento sendo necess?ria a aplica??o de antioxidantes. Nesta tese, um estudo cin?tico experimental baseado no consumo de diferentes antioxidantes sint?ticos adicionados em distintas concentra??es foi realizado com amostras de ?leos vegetais de moringa (Moringa oleifera) e de maracuj? (Passiflora edulis), ?cido ol?ico estocado (AO) durante seis e dezoito meses e biodiesel de soja (Glycine max L.) e girassol (Helianthus annuus) em diferentes temperaturas, a uma press?o de oxig?nio puro a 700 kPa, utilizando a metodologia ASTM D7545 (PetroOXY). O modelo de primeira ordem obtido para o ?leo de moringa, amostras de ?cido ol?ico estocado (AO) e biodiesel de soja permitiu obter informa??es a respeito de par?metros, tais como: concentra??o cr?tica e concentra??o de antioxidante natural inerente ? amostra avaliada , informando que o ?ltimo n?o exerceu influ?ncia, a n?o ser inicialmente, no processo oxidativo das mesmas. Enquanto, o par?metro determinado para o modelo de ordem zero para as amostras de ?leo de maracuj? e girassol relacionou-se a diferentes reatividades da mat?ria-prima. A estabilidade das amostras determinadas pela entalpia de ativa??o (?HA) deu-se na seguinte ordem: ?HA (?leo de moringa) > ?HA (?leo de maracuj?); ?HA (AO 6 meses) ?HA (AO 18 meses) e ?HA (biodiesel de soja) > ?HA (biodiesel de girassol). Fatores de estabiliza??o desempenharam diferentes pap?is na estabiliza??o dos sistemas estudados. Concentra??o de antioxidante e temperatura mostraram distintas influ?ncias, no processo oxidativo, para as amostras de ?leos vegetais e ?cido ol?ico estocadas (AO) acompanhadas pelos seus ?ndices de acidez.
Oxidative stability is a parameter included in the European standard EN 14214 and is closely associated with the quality of biodiesel. The biodiesel is usually obtained in a transterification reaction vegetable oil or animal fat. However, the composition of the raw resources biodiesel is obtained from influences the stability degree of the latter, particularly when biodiesel is stored for long periods of time, causing its degradation, thereby reducing biodiesel quality and making it inadequate for trade. In this thesis, an experimental kinetic study based on the consumption of several synthetic antioxidants added in various concentrations to vegetable oils of moringa (Moringa oleifera), passion fruit (Passiflora edulis) and oleic acid (AO) stored for six and eighteen months at the temperatures 110 ?C, 120 ?C, 130 ?C and 140 ?C, as well as biodiesel from soybean (Glycine max L.) and sunflower (Helianthus annuus) oils at the temperatures 130 ?C, 135 ?C, 140 ?C and 145 ?C at a 700 kPa pure oxygen pressure, using the ASTM D7545 Method (PetroOXY). It has been obtained a first order reaction kinetic model for oleic acid, soybean biodiesel and moringa oil samples, while for passion fruit oil and sunflower biodiesel samples a zero order reaction kinetic model has been obtained. Parameter 0,CICCCC??? determined for the zero order model was related to distinct composition variations of the raw resources. The stability order of samples established using activation enthalpy (?HA) was the following: ?HA (moringa oil) > ?HA (Passion fruit oil); ?HA (oleic acid stored for six months) ? ?HA (oleic acid stored for eighteen months) and ?HA (soybean biodiesel) > ?HA (sunflower biodiesel). In all evaluated temperatures except for 140?C, acid numbers for passion fruit oil with antioxidants added have increased after storage, while for the moringa oil a random behavior has been observed.

Finding alternatives to animal and saturated fats is an attractive challenge in bakery. In a first part of the research, effects of fat melting characteristics and fat quantity in a plum cake formulation were studied by a Central Composite Design (CCD), using palm oil/palm olein blends as fat. Cakes produced with butter (BC) or anhydrous butter (ABC) were taken as the references. Response surface models demonstrated that cake texture was significantly affected (p<0.01) both by fat content and percentage of olein in the fat blend, while volume was influenced (p<0.01) only by fat content. An optimized cake formulation (OF) was obtained. The rheology of OF, BC and ABC fats (and the corresponding batters) was studied, as well as cake characteristics during storage. Fat properties influenced batter viscoelastic behaviour and creaming performances. A higher content of unsaturated fatty acids improved baking performances: OF containing 19.7% olein in the fat blend attained good structural properties, suggesting that an aerated structure can be achieved even with a minimal solid fat content. In a second part, the effect of structured fats in plum cake was studied, using an organogel (OG) made of sunflower oil, with β-sitosterol and γ-oryzanol as gelators. OG showed higher G' with increasing gelators concentration. From the results of a CCD (with OG content in cake and gelators percentage in OG as factors), OG properties showed no significant impact (p>0.05) on the final cake, although the reference cake, produced with liquid sunflower oil, showed higher consistency (p>0.05). During storage trials, OG cakes showed slight different behaviour but further study on OG structuring in cake is needed.

Oxidative stress and inflammation are important factors involved in the progression of heart failure. An important cytokine produced during myocardial infarction (MI) is tumor necrosis factor alpha (TNF-α). TNF-α may induce oxidative stress, cell damage, apoptosis and cardiac dysfunction. Considering the anti-inflammatory and anti-oxidant properties of extra-virgin olive oil and its major component (80%) oleic acid (OA), and their benefits to the cardiovascular system, we hypothesized that the negative effects of TNF-α in the pathogenesis of heart failure will be mitigated by olive oil consumption. This hypothesis was tested by examining the effects of a special diet supplemented with 10% olive oil, in coronary artery ligated animal model of MI. Corn oil (10%) supplementation was used as a control for matching caloric intake. Animals in the sham and ligated groups fed regular chow, olive oil, and corn oil were studied at 4 and 16 weeks post myocardial infarction (PMI). Mortality, diet consumption, weight gain and conduction system abnormalities were comparable among all ligated groups. Echocardiography showed that MI deteriorated cardiac function, and olive oil restored the function. At 16 weeks PMI, only corn oil fed groups showed significant increase in both total cholesterol and HDL. Corn oil was not able to offer protection to the heart, suggesting that the beneficial effects of olive oil are not due to increased caloric intake or increased HDL. MI increased myocardial TNF-α, oxidative stress, lipid peroxidation, pro-apoptotic protein expression (Bax, cleaved Caspase 3, cleaved PARP, TGFβ, Bnip3), cytochrome C release, MAP kinase activation (p38, JNK) and decreased anti-apoptotic protein Bcl-xL expression at both 4 and 16 weeks PMI, and these changes were modulated by olive oil. In order to further test the central role of TNF-α PMI, we examined the possible miti-gation of TNF-α induced changes by OA in isolated adult rat cardiomyocytes. TNF-α in-creased oxidative stress, cell damage, cell death, and apoptosis, while OA treatment miti-gated these TNF-α induced effects. We concluded that TNF-α is implicated in the progression of heart failure subsequent to MI and that OA in olive oil may prevent this progression, through its anti-oxidant, anti-inflammatory, anti-hypertensive, and inotropic effects.

Les réactions de déshydrogénation oxydante du propane et de l’éthane ont été étudiées respectivement sur des catalyseurs à base d’oxydes alcalino-terreux (OAT) dopés néodyme et des catalyseurs à base d’oxyde de nickel dopés par différents métaux. Deux méthodes de préparation des solides OAT dopés au néodyme ont été comparées. La caractérisation par analyses DRX montre la formation de solutions solides avec des défauts (lacunes, dislocations). La formation d’agglomérats de néodyme a été également observée. Les tests catalytiques réalisés montrent que le dopage au néodyme augmente la conversion du propane avec simultanément une augmentation de la sélectivité. Les catalyseurs à base d’oxyde de nickel sont eux très actifs dans la réaction de déshydrogénation oxydante de l’éthane. L’étude réalisée montre l’absence de formation de solutions solides étendues avec les dopants. L’addition de niobium et des ions oxalates permet l’isolation des sites actifs qui sont des ions O- et entraine une baisse d’activité mais conjointement une forte amélioration de la sélectivité en éthylène. De plus, elle modifie la texture de NiO en augmentant sa surface spécifique ce qui permet d’obtenir de meilleures conversions. La mise au point de ces catalyseurs est compromise par une désactivation: la caractérisation des solides avant et après désactivation par DRX, Raman, XPS, TEM, EDX et TPD de O2 montre que cette désactivation est due à la réduction lente et irréversible des ions Ni3+ entrainant la diminution du nombre des espèces O-. La formation de la phase NiNb2O6 lors de la désactivation a été également observée
The oxidative dehydrogenations of propane and ethane have been studied on alkaline earth oxides doped with neodymium oxide (AEO) and nickel oxide doped with different metal oxides. Two types of synthesis have been compared for the preparation of AEO+Nd samples. The characterization by XRD showed the formation of solid solutions with different defects (cationic vacancies, dislocations). The formation of agglomerates of neodymium has also been observed. The catalytic testing showed that the presence of neodymium oxide increases both the conversion of propane and the selectivity to propylene. The addition of neodymium oxide increases the basicity of the catalysts, which seems to be beneficial to the selectivity. The nickel oxide based catalysts are very efficient in the oxidative dehydrogenation of ethane. The study shows that there is no formation of extended solid solution. The addition of niobium and oxalates anions leads to the isolation of the active O- sites at the surface of the nickel oxide, which decreases the activity but strongly increases the selectivity to ethylene. Furthermore, it modifies textural properties of nickel oxide increasing its specific surface area leading to better conversions. However, the applicability of this type of catalysts stays under question because of a deactivation that has been evidenced with time on stream. The characterization of the fresh and deactivated catalysts by XRD, Raman, XPS, TEM, EDX and TPD of O2 showed that this deactivation is due to the slow and irreversible reduction of Ni3+ cations leading to a further decrease in number of the O- species. The formation of NiNb2O6 phase during the deactivation has been evidenced

Cette thèse s'est intéressée à la synthèse de complexes de cuivre(III) et à l'étude de leur réactivité vis-à-vis des étapes élémentaires composant les cycles catalytiques des processus d'oligomérisation d'oléfines (insertion migratoire, ß-H élimination/transfert, isomérisation, couplage oxydant). Dans ce but, une méthodologie combinant calculs théoriques et tests expérimentaux a été exploitée. Le premier chapitre de cette thèse présente de manière générale l'oligomérisation d'éthylène pour la formation d'a-oléfines linéaires et explique l'intérêt d'utiliser un catalyseur à base de cuivre d'un point de vue industriel et fondamental. D'après les calculs théoriques prédictifs réalisés, l'insertion migratoire dans une liaison Cu(III)-C semble plus accessible que dans une liaison Cu(I)-C. Le premier verrou de cette thèse est donc l'accès à ces complexes de cuivre(III). Le deuxième chapitre expose de façon générale la chimie du cuivre et son utilisation en catalyse. De façon plus approfondie, une étude bibliographique sur les complexes de cuivre(III) stables est reportée afin de comprendre quels critères aident à la stabilisation de ces complexes. Les espèces de cuivre(III) étant connues pour être très instables, les techniques expérimentales utilisées pour la détection de ces espèces hautement réactives sont également décrites. En revanche, les complexes organométalliques de cuivre(III) connus et stables ne conviennent pas à la réactivité envisagée. En s'appuyant sur des calculs théoriques ainsi que sur les résultats précédemment obtenus dans le groupe sur la chimie de l'or, deux stratégies, décrites dans les chapitres trois et quatre, ont été envisagées pour obtenir un complexe de cuivre(III) stable. Le troisième chapitre de cette thèse traite de la première stratégie pour l'accès à des complexes de cuivre(III) basée sur l'addition oxydante C-I intramoléculaire assistée par un effet chélate. Des études théoriques ont été menées et les ligands naphthylphosphine et naphthylamine péri-iodée ont été choisis. Des couplages C-Br, C-C et C-P ont été observés et permettent de supposer un intermédiaire de cuivre(III). La formation originale et inédite d'un phosphonium cyclique péri-ponté est constatée. Des conditions catalytiques ont été mises au point ainsi que l'activation de liaisons moins réactives (C-Br et C-Cl). La réouverture du cycle par addition oxydante à l'or est également observée. Le quatrième chapitre porte sur la deuxième stratégie d'accès au complexe de cuivre(III), l'addition oxydante intermoléculaire à partir d'un complexe de cuivre(I) coudé, porteur d'un ligand bidente LX. Le choix des ligands ß-dikétiminates a été fait en accord avec les calculs théoriques prédictifs. La non-innocence de ces ligands a conduit à leur modification. Les anilido-imines ont constitué une alternative intéressante permettant de former des complexes p de cuivre(I) avec des alcènes et des diènes-1,3. Le cinquième chapitre a pour objet la synthèse de complexes anilido-imines d'or(I) et l'étude de leur réactivité vis-à-vis de l'addition oxydante. Les complexes d'or(III) sont plus stables que les complexes de cuivre(III), la formation de nouveaux complexes d'or(III) peut permettre de mieux appréhender la stabilisation du cuivre(III)
This thesis focused on the synthesis of copper(III) complexes and the study of their reactivity toward the elementary steps induce in catalytic cycles of olefin oligomerization processes (migratory insertion, β-H elimination/transfer, isomerization, oxidative coupling). For this purpose, a methodology combining theoretical calculations and experimental tests was used.The first chapter of this thesis presents in general oligomerization of ethylene for the obtaining of linear α-olefin and explains the interest of using a copper catalyst from an industrial and fundamental point of view. According to the predictive theoretical calculations performed, the migratory insertion process in a Cu(III)–C bond seems more accessible than in a Cu(I)–C bond. The first lock of this thesis is therefore access to these copper(III) complexes.The second chapter gives a general overview of copper chemistry and its use in catalysis. In more depth, a bibliographic report on stable copper(III) complexes is reported in order to understand which criteria help stabilize this complexes. Copper(III) species being known to be very unstable, the experimental techniques used for the detection of these highly reactive species are also described. On the other hand, the known and stable organometallic copper(III) complexes are not suitable for the reactivity envisaged. Based on theoretical calculations as well as on the results previously obtained in the group on gold chemistry, two strategies described in chapters three and four, were considered to obtain a stable copper(III) complexes.The third chapter of this thesis deals with the first strategy for access to copper(III) complexes based on intramolecular C–I oxidative addition assisted by a chelate effect. Theoretical studies were carried out and the naphthylphosphine and naphthylamine peri-iodide ligands were chosen. C–Br, C–C and C–P couplings have been observed and allow to suppose a copper(III) intermediate. The original and unprecedented formation of a cyclic peri-bridged phosphonium is observed. Catalytic conditions have been developed as well as the activation of less reactive bonds (C–Br and C–Cl) were developed. The reopening of the ring by oxidative addition to gold is also observed.The fourth chapter deals with the second access strategy for the copper(III) complex, intermolecular oxidative addition from a bent copper(I) complex, carrying an LX bidente ligand. The choice of β-diketiminate ligands was performed in accordance with the predictive theoretical calculations. The non-innocence of these ligands led to their functionalization. Anilido-imines have constituted an interesting alternative allowing the formation of copper(I) π-complexes with alkenes and 1,3-dienes.The fifth chapter is about the synthesis of gold(I) anilido-imines complexes and the study of their reactivity toward oxidative addition. Gold(III) complexes are more stable than copper(III) complexes, the formation of new gold(III) complexes can help better understand the stabilization of copper(III) complexes

Au niveau industriel, l'accès aux acides azélaïque et pélargonique, composés à forte valeur ajoutée, est possible grâce à une réaction d'ozonolyse de l'acide oléïque. Cependant, cette méthode présente certains désavantages sur le plan écologique. Le but de cette étude a donc été de développer une méthode alternative à ce procédé industriel, visant à limiter autant que possible les impacts écologiques, directs ou indirects, lors de la synthèse des acides azélaïque et pélargonique. Nous avons ainsi montré qu'un clivage en deux étapes peut être préférable à un clivage oxydant en une étape. Notre procédé propose ainsi, dans un premier temps, une dihydroxylation de la double liaison d'acides gras par une méthode connue, laquelle est suivie par un clivage oxydant en présence d'hypochlorite de sodium. Ce nouveau procédé mis au point au sein du laboratoire présente l'avantage de ne nécessiter l'emploi ni de métaux de transition, ni de solvant organique. Nous avons par la suite étudié l'hypochlorite de sodium afin de déterminer son rôle et son mode d'action dans la réaction de clivage de diols vicinaux
Industrial production of two high added value compounds called pelargonic acid and azelaic acid is made possible by the ozonolysis reaction of oleic acid. However, this method has numerous disadvantages in term of ecological impact. In this dissertation, we present an alternative to the current industrial process in order to lower direct or indirect negative environmental impacts when synthetizing azelaic and pelargonic acids. At first we demonstrate that a two-step oxidative cleavage may be preferable to a one-step cleavage. Then we present in details a novel synthesis method which starts with the dihydroxylation of the fatty acids double bond using a well known method, followed by the oxidative cleavage in presence of sodium hypochlorite. One notes that this original fabrication process developed in our laboratory does not require to use transition metals nor organic solvents. As a complement to this work, we have subsequently studied the sodium hypochlorite to determine its role and operating mode in the vicinal diols cleavage reaction

U okviru ove doktorske disertacije ispitani su i utvrđeni optimalni uslovi za proces ljuštenja semena suncokreta visokooleinskog tipa, kao sirovine za proizvodnju ulja. Sprovedena istraživanja su dala podatke o optimalnim vrednostima sadržaja vlage u semenu i pritiska vazduha u ljuštilici na osnovu kojih je utvrđen model za ljuštenje semena. Sprovedenim istraživanjima obuhvaćeno je i ispitivanje uticaja promenljivih tehnoloških parametara, sadržaja ljuske u opsegu od 0 do 20% i sadržaja nečistoća u opsegu od 0 do 10% na sastav i kvalitet hladno presovanih ulja i pogače, prinos ulja, oksidativnu stabilnost, senzorski kvalitet i boju hladno presovanih ulja semena suncokreta visokooleinskog tipa.Dobijeni rezultati su obrađeni primenom savremenih klasifikacionih (klaster analiza i analiza glavnih kompomenata) i regresionih hemometrijskih metoda i postavljeni hemometrijski modeli čija bi primena doprinela proizvodnji hladno presovanog ulja vrhunskog kvaliteta i visoke oksidativne stabilnosti. Utvrđeno je da su definisani modeli statistički validni i da se mogu primeniti za optimizaciju tehnoloških parametara u proizvodnji hladno presovanog ulja semena suncokreta visokooleinskog tipa. Validnost postavljenih modela, odnosno kvalitet dobijenih korelacija su procenjeni na osnovu parametara unakrsne validacije.Maksimalna efektivnost ljuštenja semena suncokreta visokooleinskog tipa može se postići pri optimalnim uslovima tj. sadržaju vlage u semenu 6,0% i pritisku vazduha u ljuštilici 800 kPa. Hladno presovano ulje semena suncokreta visokooleinskog tipa se, u pogledu sastava i kvaliteta ulja i pogače, prinosa ulja, oksidativne stabilnosti, senzorskog kvaliteta i boje ulja, može proizvoditi od semena koje sadrži 10-20% ljuske i 0-5% nečistoća.
In this dissertation the optimal conditions for the dehulling process of high-oleic sunflower seeds, as raw material for oil production, were tested and determined. The conducted studies provided data for the optimal values of moisture content in the seed and the air pressure in the seed dehulling machine, what presented the base for determination of the dehulling model. Also, conducted studies examine the effect of variable technological parameters, such as content of hull (ranging from 0 to 20%) and the impurities content (ranging from 0 to 10%) on the composition and quality of oil and cake, oil yield, oxidative stability, sensory quality and colour of cold pressed high-oleic sunflower oil.The obtained results were analyzed by modern classification (cluster analysis and principal component analysis) and regression chemometrics methods, and chemometric models whose implementation could contribute to the production of cold pressed oil of high quality and high oxidative stability were set. It was found that the defined mathematical models are statistically valid and that they could be used to optimize the technological parameters of production of cold pressed high-oleic sunflower oil. The validity of the set models, that is the quality of obtained correlations, were estimated based on the parameters of cross-validation.The maximum effectiveness of high-oleic sunflower seeds dehulling can be achieved under optimal conditions, i.e. when the moisture content in seed is 6,0% and when the air pressure in seed dehulling machine is 800 kPa. Regarding composition and quality of the oil and cake, oil yield, oxidative stability, sensory quality and color, cold pressed high-oleic sunflower oil could be produced from seed containing 10-20% hull and 0-5% impurities.

Dans un contexte de raréfaction des ressources pétrolières et de pressions environnementales, l’industrie chimique a besoin d'innover en développant de nouvelles filières destinées à l'élaboration de bioproduits, à partir de matières premières d'origine végétale. Les acides gras insaturés obtenus à partir des huiles végétales, constituent ainsi une ressource renouvelable à fort potentiel permettant de diversifier les approvisionnements d'origine pétrolière. Notre intérêt s'est porté sur la réaction de scission oxydative d’acides gras insaturés pour conduire à des monoacides et diacides à chaînes courtes et impaires, peu ou pas disponibles à l’état naturel. Ce type de chaînes hydrocarbonées est recherché dans l’industrie, car elles possèdent des propriétés spécifiques, mais elles ne sont actuellement produites qu'à partir de ressources fossiles. L'objectif était donc de mettre au point un procédé de clivage oxydatif performant, moins onéreux et moins polluant que l’ozonolyse, le seul procédé industriel opérationnel. Les conditions oxydantes sélectionnées font appel à l’eau oxygénée en tant qu’oxydant, associée à un catalyseur de transfert de phase, sans avoir recours à un solvant organique. Plusieurs catalyseurs de transfert de phase Q3{PO4[WO(O2)2]4} ont été préparés à partir de l’acide tungstophosphorique, d’eau oxygénée et d'un sel d’ammonium quaternaire (Q+,Cl-), afin de comparer leur efficacité à transférer l'oxygène vers le substrat en phase organique. Une optimisation des paramètres réactionnels a été effectuée avec le catalyseur le plus performant. De plus, deux protocoles ont été mis au point, pour la préparation in-situ du catalyseur et pour sa récupération en fin de réaction. Le procédé a été généralisé à des dérivés d’acides gras dans le but d’obtenir d'autres acides à chaînes courtes, répondant à une large gamme d'applications. Le gain environnemental lié à ce nouveau procédé a été évalué par le calcul d’indicateurs verts. Afin d’envisager un recyclage plus aisé du catalyseur, l’anion oxodiperoxotungstate {PO4[WO(O2)2]4}3-, l’espèce active du catalyseur, a été supporté sur des résines échangeuses d’anions. Deux types de résines macroporeuses ont été testées : des résines commerciales (Amberlite IRA 900 et Lewatit K7367) et des résines modifiées (type Merrifield). Nous avons montré que ces dernières conduisent à de meilleurs rendements de scission oxydative de l’acide oléique que les résines commerciales, et ce, malgré la présence de solvants. Cependant, l’immobilisation de l’anion oxodiperoxotungstate sur les résines commerciales a permis la synthèse en une seule étape d’acétals, composés présentant un grand intérêt pour la synthèse de dérivés à haute valeur ajoutée. En utilisant l’acétone, à la fois comme réactif et solvant, nous avons obtenu de bons rendements en cétal. De plus, la réaction d’acétalisation « one-pot » de l’acide oléique a pu être étendue à d’autres solvants (alcools), offrant la possibilité de synthétiser un large panel d’acétals. Le procédé développé est particulièrement intéressant car il conduit directement à la synthèse d’acétals ou de cétals à partir d’un acide gras insaturé biosourcé, en évitant les étapes de réactions intermédiaires
In a context of scarce oil resources and environmental pressures, the chemical industry needs to innovate by developing new production chains aiming the design of bioproducts from biobased raw materials. Unsaturated fatty acids derived from vegetable oils, thus represents renewable resources with a great potential, allowing to diversify petroleum based supplies. Our interest is focused on the oxidative cleavage reaction of unsaturated fatty acids to yield mono-acids and di-acids with shorter and odd hydrocarbon chains, which are not available at a natural state. Such hydrocarbon chains are attractive for industry because they meet specific properties. But, they are currently only produced from fossil resources. Therefore, the objective was to develop an efficient method for oxidative cleavage, less expensive and less polluting than ozonolysis, the only operational industrial process. The selected oxidizing conditions employs hydrogen peroxide as oxidant, together with a phase transfer catalyst, without using an organic solvent. Several phase transfer catalysts Q3{PO4[WO(O2)2]4} were prepared from tungstophosphoric acid, hydrogen peroxide and a quaternary ammonium salt (Q+,Cl-), in order to compare their effectiveness in transferring oxygen to the substrate in the organic phase. An optimization of reaction parameters was carried out with the most performing catalyst. In addition, two protocols have been developed for the in-situ preparation of the catalyst and its recovery after reaction. The method was extended to fatty acids derivatives, in order to obtain other short chain acids, having a wide range of applications. The environmental benefits associated with this new method were evaluated by calculating green indicators. To consider an easier recycling of the catalyst, the oxodiperoxotungstate anion {PO4[WO(O2)2]4}3-, the active species of the catalyst was supported on anion-exchange resins. Two types of macroporous resins were tested: commercial resins (Amberlite IRA 900 and Lewatit K7367) and modified resins (type Merrifield). We showed that the modified resins, lead to the oxidative cleavage of oleic acid with higher yields than commercial ones, despite the presence of solvent. However, the immobilisation of the oxodiperoxtungstate anion on commercial resins allows the one-step synthesis of acetals, compounds of great interest for the synthesis of derivatives with a high added value. Using acetone as both reagent and solvent, we obtained good yields in ketal. Furthermore, the "one-pot" acetalization reaction of oleic acid was extended to other solvents (alcohols) as an opportunity to synthesize a wide range of acetals. The developed process is particularly interesting as it leads to the direct synthesis of ketal or acetals from an unsaturated fatty acid, avoiding the intermediate reaction steps