Dissertations / Theses on the topic 'Fonctionnalisation directe C—H'
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Rey-Rodriguez, Romain. "Fonctionnalisation directe métallo-catalysée de liaison C-H d’énamides." Thesis, Orléans, 2016. http://www.theses.fr/2016ORLE2005/document.
Full textThe aim of this Ph.D thesis was the development of new synthetic methods for the metal-catalysed direct CH functionalization of enamide with chemo-, regio- and possible enantioselectivity. First, we have developped a C3-selective trifluoromethylation of enamide with Fe (II) catalyst involving new sources of fluoride (Togni’s reagent II) with a radical mechanism. Secondly, two new synthetic methods with Fe(II) and Fe(III) were promoted for the selective azidation of enamides respectively at C2 and C3 position involving difunctionalization of the C=C double bond. β-azido alcohols and α-azido esters were then synthesized by controlling the diastereoselectivity for the trans isomer. Finally, studies on the reactivity of nitrenes on enamides allowed us to develop oxyamidation reaction and CH amination with a selective insertion of nitrenes respectively on the double bond C=C or at C4 position. The outcome of the reaction is highly substrate-dependent and several γ-amino enamides and β-amino ethers have been synthesized
Sahnoun, Sophian. "C-H fonctionnalisation de purines : synthèse d’inhibiteurs potentiels de la HSP90." Thesis, Paris 11, 2011. http://www.theses.fr/2011PA114803/document.
Full textResistance to current treatments of cancer encourages finding new therapeutical targets. The heat shock protein 90 (hsp90) is a molecular chaperon which regulates the folding of many client proteins associated with all of the six hallmarks of cancer, and helps maintaining their proper conformation. Consequently, the hsp90 has become an exciting new target in cancer drug discovery since the inhibition of its ATPase activity leads to depletion of these client proteins via the proteasomal pathway. PU3 and PU24S are purine-based hsp90 inhibitors functionalized on C-8 position. In the aim to identify more active compounds and/or new subfamilies of inhibitors, we have developed new metal-catalyzed C-H activation processes of various heterocycles including purines and other azoles. These new and simple approaches have allowed the access to numerous C-8 functionalized purines bearing (het)aryl, alkenyl and benzyl moieties
Sahnoun, Sophian. "C-H fonctionnalisation de purines : synthèse d'inhibiteurs potentiels de la HSP90." Phd thesis, Université Paris Sud - Paris XI, 2011. http://tel.archives-ouvertes.fr/tel-00692582.
Full textVabre, Roxane. "Fonctionnalisation directe de liaisons C-H et couplages croisés pour la formation de liaisons C-C et C-N : synthèse de purines 6,8,9-trisubstituées." Phd thesis, Université Paris Sud - Paris XI, 2013. http://tel.archives-ouvertes.fr/tel-00923198.
Full textNaturale, Guillaume. "Approches radicalaires pour la fonctionnalisation directe de quinones à visée anticancereuse." Thesis, Bordeaux 1, 2012. http://www.theses.fr/2012BOR14635/document.
Full textIn our ongoing course dedicated to the discovery of small anticancer molecules, we designed novel quinone derivatives. Our first objective was to fashion non-peptidic Smac mimics, able to trigger apoptosis in tumor cells, displaying a structure rigidified by conformational restrictions. Otherwise, the kinases and the phosphatases, acting as phosphorylating / dephosphorylating agents mostly in the control of the cell cycle, were thought to be other relevant biological targets. An intent study of their known inhibitors allowed us to underline trends in their chemical structure and made us plan the synthesis of functionalized naphthoquinones.A dedicated approach involving radical decarboxylation of amino acids allowed the introduction of aliphatic side chains on our substrates though C(sp2)–C(sp3) bond formation. Ag(I)/S2O82- was used as alkyl radical initiator and the direct C-H alkylation of the quinonic positions could take place. C(sp2)–C(sp2) bonds were created through aryl radicals generation from stable diazonium salts or anilines which allowed the direct C-H arylation of quinones. The procedures described along this manuscript let us formulate several advances on the substrates reactivity and on the reaction mechanisms involved
Baladi, Tom. "Autour du noyau imidazo[4,5-b]pyridine : inhibiteurs potentiels de la protéine kinase Tyro3 et fonctionnalisation directe de liaisons C – H." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLS386/document.
Full textBladder cancer is a major medical issue, being the fourth most frequent cancer in men and treatable only with heavy surgery and/or broad-spectrum chemotherapy. This thesis project deals with the discovery of new targeted therapies of bladder cancer by blocking specifically, at a molecular scale in cancer cells, the signaling pathways in which protein kinase Tyro3 is involved. Indeed, its overexpression in most bladder cancers and the major part it plays in cancer cells survival have led to the validation of protein kinase Tyro3 as a therapeutic target for the treatment of bladder cancer. This thesis project can be divided into three main parts: the development of new synthetic methods around the imidazo[4,5-b]pyridine scaffold, the synthesis of a library of compounds using these methods and eventually the study of structure-activity relationships of these compounds versus Tyro3
Collado, Ruiz Sandra. "Palladation et fonctionnalisation de pyrimidinones et d'imidazolones." Thesis, Normandie, 2018. http://www.theses.fr/2018NORMIR21/document.
Full textSince past decade, our laboratory is concerned with transition-metal catalyzed C-H functionalization of heterocycles. A recent research program is dedicated to the class of N-acyl amidine pro-aromatic heterocycles. This present thesis work is first directed to the pyrimidin-4-one series that remains highly sparsely evaluated. As main results, Pd(0)-catalyzed and Cu(I)-assisted C2-H arylation of pyrimidin-4-one flanked with picolinyl and other ortho-directed groups at the nitrogen atom was set up using arylhalides as coupling partners. The C5-substituted pyrimidin-4-ones were also evaluated. To pursue recent investigations in 4-alkyl and 4-arylidene imidazolone series leaing ding to innovative GFP probes, the second work aims at evaluating the first step of an ultimate intramolecular C-H/C-H coupling to stiffen the 4-arylidene imidazolone core. For that, the intramolecular ortho-palladation was achieved in collaboration with Dr. Esteban Urriolabeitia of the University of Zaragoza in Spain providing a broad panel of original imidazolone-based palladacycles. Their photophysical properties were determined and their reactivity towards cross-coupling as well as oxidating agents were also evaluated
Muselli, Mickaël. "Synthèse et fonctionnalisation directe catalytique de la liaison C-H d'imidazolones : nouvel accès aux fluorophores analogues de la GFP." Thesis, Normandie, 2017. http://www.theses.fr/2017NORMIR10/document.
Full textImidazolones have been studied for a long time, either as bioactive molecules or for their fluorescence properties, the best known example being the Green Fluorescent Protein or GFP. Numerous syntheses are already described, in particular the condensation of an amine with an oxazolone (Erlenmeyer method). In this work, we not only improved the condensation protocol but also developed an original synthesis consisting in using 2-H imidazolones CH arylation. To this end, it was first necessary to develop a protocol for the synthesis of 2-H imidazolones, hitherto very little described, and then to develop the conditions for arylation and direct vinylation of these molecules. Two sets of imidazolones have been studied and published separately: first, the 4,4'- dialkylimidazolones, frequently used for their biological properties, followed by arylation and vinylation of 4-arylidene-2-H imidazolones
Zhao, Qun. "Palladium-catalyzed directed introduction of α-CF3-vinyl and SCF3 groups by C-H bond functionalization." Thesis, Normandie, 2017. http://www.theses.fr/2017NORMIR15.
Full textRecent years have witnessed a great development of the organofluorine chemistry field. In particular, the introduction of emergent fluorinated moieties onto various scaffolds has attracted attention of the scientific community because of their special properties. Besides, transition metal-catalyzed directed C-H bond functionalization strategy has brought a revolution in the development of original synthetic methodologies, since it allows straightforward and more atom-economical processes. Thus, the design of new synthetic approaches for the introduction of fluorinated moieties by transition metal-catalyzed C-H bond functionalization pathway is particularly appealing. Therefore, in this Ph.D. thesis, we focused on the development of new methodologies for the direct introduction of fluorinated moieties onto arenes and olefins by transition metal catalyzed directed C(sp2)-H bond functionalization. In particular, we turned our attention to the 2-bromo-3,3,3-trifluoropropene (BTP), an inexpensive fluorinated reagent coming from industry waste, used as a potential halon replacement for fire suppression and as a fluorinated building block in organic synthesis (Chapter 1). The first part of this Ph.D. thesis was dedicated to the development of new methodologies for the direct introduction of a CF3- vinyl moiety onto arenes and olefins by a Pd-catalyzed directed C(sp2)-H bond functionalization with BTP. Then, this approach was extended to the functionalization of α,β-unsaturated esters, although a different reaction pathway is probably involved (Chapter 2). In the second part of this Ph.D. thesis, we developed a new methodology for the direct introduction of the SCF3 group onto arenes and olefins by Pd-catalyzed directed C(sp2)-H bond functionalization using the Munavalli reagent (Chapter 3)
De, Robichon Morgane. "Accès à des C-glycosides par fonctionalisation C-H métallo-catalysée de la position anomère orientée par un groupement directeur." Electronic Thesis or Diss., CY Cergy Paris Université, 2021. http://www.theses.fr/2021CYUN1049.
Full textGlycoconjugates are ubiquitous in living organisms and are involved in a wide range of biological processes, such as cell adhesion or cell recognition. Considering the importance of these compounds, chemists are increasingly synthesizing these structures of interest and their analogues. In particular, C-arylglycosides have proven to be excellent drug candidates, as illustrated by the gliflozin family, six members of which are known to treat type 2 diabetes. Functionalization of C-H bonds is an effective and emerging method of transformation. Given the large number of C-H bonds in complex substrates, the use of strategically placed directing groups (DG) overcomes the regioselectivity issues inherent in activating a specific C-H bond. However, examples of metal-catalyzed C-H functionalization (MCF) on sugars are still scarce and MCF of Csp2-H bonds remain more developed than Csp3-H.The first part of the project focuses on the metal-catalyzed Csp2-H functionalization of glycals (sugars with an intracyclic double bond) directed to the pseudo-anomeric position (position 1). The prior introduction of a DG at position 2 of various glycals allowed the development of a palladium-catalyzed C-H arylation, affording 20 examples in excellent yields. Subsequently, C-alkynylglycosides could be synthesized by nickel-catalyzed C-H alkynylation, using the same strategy. These compounds were engaged in a click reaction leading to glycoconjugates. In both methodologies, the protecting groups could not be removed, but two methods to cleave the DG are proposed. Finally, a carbonylative C-H arylation methodology was initiated during this thesis.The second part of the project concerns the development of C-glycosides from saturated glycopyranosides via a MCF of a tertiary anomeric Csp3-H bond. To target the anomeric site, we chose to place the DG at position 1. Starting substrates with different types of directing groups could already be synthesized, but the functionalization of the anomeric C-H bond by an intermolecular process has not been conclusive so far
Li, Haoran. "Pd-catalyzed C-H bond functionalizations of (hetero)arenes and alkenes : A one step access to poly(hetero)aromatics and styrene derivatives." Thesis, Rennes, Ecole nationale supérieure de chimie, 2020. http://www.theses.fr/2020ENCR0068.
Full textIn order to explain the background of my research work, in the first chapter, I summarized general mechanistic information on palladium-catalyzed C-H bond arylation and detailed some literature on direct arylation related to my research work. My objectives were to study the reactivity of new synthetic units allowing the straightforward access to bi-(hetero)aryls compounds or styrene derivatives using aryl halides or benzenesulfonyl chloride derivatives as the aryl-sources. Then, in the chapters 2-6, I summarized my research work. I studied the regiocontrolled palladium-catalyzed direct C2-arylations of Methoxsalen using benzenesulfonyl chlorides and C2,C3-diarylations using aryl bromides as the aryl sources. These results are summarized in the chapter 2. Then, I found that Pd-catalyzed direct arylation reaction allows the easy access to Ticlopidine derivatives arylated at the C5-position of the thienyl ring in one step. These results are reported in the chapter 3. In the chapter 4, we studied the reactivity of Diflufenican which contains a 1,3-difluorobenzene ring and a pyridine unit using Ru and Pd catalysis. Under appropriate conditions, two different C-H bonds of Diflufenican could be arylated. In the chapter 5, I employed different aryl sources to functionalize the C10- and C11-positions of dibenzo[b,f]azepines, and obtained asymmetric products. Through these reactions, a wide diversity of functional group were introduced on the dibenzo[b,f]azepine derivatives. Finally, in the Chapter 6, I report the first method allowing to prepare C10-arylated Cyproheptadine derivatives
Verrier, Cécile. "Etude des nouvelles méthodologies de fonctionnalisation directe palladocatalysées de la liaison C-H en série oxazole-4-carboxylate : application à la synthèse de molécules naturelles et de sondes fluorescentes oxazoliques." Phd thesis, INSA de Rouen, 2010. http://tel.archives-ouvertes.fr/tel-00577109.
Full textPanza, Florian. "Fοnctiοnnalisatiοn directe οrthοgοnale métallο-catalysée des sites carbοne-hydrοgène des platefοrmes pharmacοlοgiques à cοeur imidazοisοindοle." Electronic Thesis or Diss., Normandie, 2024. http://www.theses.fr/2024NORMIR11.
Full textFor several decades, chemists constantly seek to push the limits of synthetic strategies by developing ever more efficient and more economical methodologies. In this context, transition metal-catalyzed direct functionalization of C—H bonds is one of the most powerful tools for constructing and funtionalizing simple molecules and ever more complex moieties, with a great diversity of C—H bonds. These strategies also answer the needs for the opening of the chemical space of functionalization. Imidazoisoindole, tricyclic heterocycle composed of an imidazole core, is a very interesting scaffold for biological activity and presents C—H bonds with very diverse properties, but late-functionalization methodology of these structures has yet to be listed in the literature. This work takes place in this context and presents, (I) based on past laboratory experience, a robust methodology to synthetize diversely substituted imidazoisoindoles at high scale by palladium-catalyzed intramolecular C—H activation ; (II) an extension of standard directC2—H functionalization of 1,3-diazole moieties applied to imidazo[5,1-a]isoindoles with a palladium(0)-copper(I) cooperative catalysis ; (III) a new methodology of direct C(sp³)—H palladium-catalyzed mono-functionalization at benzylic position of imidazo[2,1-a]isoindoles ; (IV) a preliminary study of the observed regioselectivity of iridium-catalyzed direct C(sp²)—H borylation of imidazo[2,1-a]isoindoles
Theveau, Laure. "Traitement de la sélectivité en fonctionnalisation directe catalytique de la liaison C-H d'hétérocycles - Etude en séries oxa(thia)zole-4-carboxylate et application à la synthèse de composés d'intérêt biologique." Rouen, 2013. http://www.theses.fr/2013ROUES033.
Full textHedouin, Jonathan. "Etude de cascades réactionnelles pallado-catalysées de fermeture d’allènamides et d’allylation directe de liaisons C-H et C-CO2H d’azoles, d’énamides et d’acides propioliques pour la diversité structurelle." Thesis, Normandie, 2017. http://www.theses.fr/2017NORMIR21/document.
Full textThe design of efficient and eco-friendly atom and step-economical synthetic plans of molecules using highly available starting materials is one of major objectives of organic chemist. Transition metal catalysis has allowed a bold step to build and functionalize consecutively, through a one-pot reaction, major nitrogen-containing heterocycles which are broadly present into numerous natural products, pharmaceutics and agrochemicals. The catalysis is based upon tandem inner-sphere elemental chemical transformations and one of major current challenge is to implement catalytic metallation of C-CO2H and C-H bonds. Involved in this young field of research initiated since the past decade from sevaral groups including pioneering and high active Jieping Zhu team of the Polytechnic School of Lausanne, the present study has been directed towards the design of innovative palladium-catalyzed domino Grigg nitrogen-containing heterocycles building through ortho-halogeno allenamides intramolecular carbopalladation process followed by direct C-H allylation of heterocycles and enamides or direct decarboxylative allylation of propiolic acids. After demonstrating the reactivity of nitrogen-conjugated pi-allypalladium complex in direct C-H allylation of acidic heterocycles, first palladium-catalyzed tandem build and heteroarylation of 1(2H)-isoquinoleinone and indole from ortho-halogeno allenamides was first envisaged. Efforts were next directed to the setting up of a one-pot protocol including in situ generation of allenamide followed by palladium-catalyzed domino building and functionalization of heterocycles. It was then hugely evaluated to the preparation of indole, 1(2H)-isoquinoleinones, isoquinolins as well as high-membred ring heterocycles such as benzo-(2H)-azepine and benzo-(2H)-azocine embedding with oxadiazoles and oxa(thia)zoles. An first extended synthetic concept towards the palladium-catalyzed tandem build and propargylation of nitrogen-containing heterocycles using sevral propiolic acids as coupling partners
Zakis, Janis Mikelis. "Catalyseurs d'iridium cyclométallés pour la borylation ortho-dirigée de C–H." Electronic Thesis or Diss., Strasbourg, 2024. http://www.theses.fr/2024STRAF006.
Full textC–H borylation has continued to evolve from early examples of stoichiometric reactions to a method employed for building block synthesis on a kilogram scale. However, challenges remain for its wider application. We have developed new bis-cyclometallated iridium complexes exhibiting an improved reactivity and air-stability. These complexes have been used for the ortho-directed C–H borylation of arenes, heterocycles, and acrylamides, achieving average to high yields. By combining these new catalysts with high-throughput screening, we rapidly evaluated the reactivity of different directing groups, enabling predictions for the functionalization of substrates with multiple directing groups. Mechanistic studies revealed the details how these new bis-cyclometallated complexes are activated during the reaction. Subsequently, we investigated ligand free borylation and found a wide range of compatible substrates. We then investigated miniaturization of C-H borylation reactions and successfully conducted them on micromolar scale. By integrating our findings with those from the literature, we designed a screening platform comprising eight different reaction conditions. This platform was used to screen a vast array of small molecules, as well as more complex substrates. The results revealed differences between the catalytic systems and allowed us to successfully functionalize complex molecules. These findings highlight the widespread of ligand-free borylation as well as the limitations of the current state-of-the-art methods
Roudesly, Fares. "Fonctionnalisation C-H dirigée d'hétérocycles azotés." Thesis, Sorbonne université, 2018. http://www.theses.fr/2018SORUS354.
Full textThis thesis work has brought its contribution the field of C-H activation / functionalization of nitrogenous containing rings as pyridine and pyrrole. First, we developed a strategy for a Pd- catalyzed regioselective allylation and alkenylation of azine N-oxides. The scope of this reactivity has been studied. Experimental studies and DFT calculations allowed us to propose a mechanism for the allylation and isomerization steps. We propose that the C-H activation step is the rate determining step of the catalytic cycle, and that it takes place through an outer sphere deprotonation / palladation mechanism. Next, we applied the Murai reaction to 2-pyrrole- carboxaldehyde derivatives using a Ru(0) complex. Under an atmospheric pressure of carbon monoxide, we could obtain the acylated products in the presence of various vinylsilanes and styrenes. The application of this reactivity to other 2-pyrrole carboxaldehyde derivatives is under study in the laboratory
Thongpaen, Jompol. "Ligands NHCs bifonctionnels en fonctionnalisation C-H métallo-catalysée." Thesis, Rennes, Ecole nationale supérieure de chimie, 2019. https://www.ensc-rennes.fr/formations/doctorats.
Full textThe direct functionalization of inert CH bonds has emerged over the past two decades as an increasingly important synthetic tool. In particular, transition metal (TM)-catalyzed C-H functionalization has witnessed continuing improvements in performance, allowing expansion of the toolbox available for organic material synthesis, natural products synthesis, and drug-discovery programs. In spite of this success, there is still a need for the development of methodologies to efficiently enable C-H bond transformation under mild conditions. During the past two decades, N-heterocyclic carbenes (NHCs) have become ubiquitous ligands in coordination chemistry and catalysis. Their unique properties, including strong σ- donation, are responsible for forming robust TM catalysts that allow for the development of more efficient synthetic procedures. Nevertheless, the use of NHC ligands in transition metal-catalyzed C-H functionalization has remained limited. Because organoboron compounds are versatile intermediates in synthetic chemistry, the development of new catalytic systems for selective borylation of unactivated C-H bonds would afford new perspectives in organometallic and catalysis. Herein, this Thesis discloses an efficient and straightforward strategy to access various types of transition metal complexes bearing bidentate NHC-carboxylate ligands which were fully characterized including solid-state structures. These unprecedented complexes possessing chelating-NHC ligands exhibited high efficiency and selectivity in site selective borylation of inert C-H bonds under mild conditions including a photosensitizer-free photocatalytic conditions
Dupont, Jairton. "Activation-fonctionnalisation intramoleculaire de liaisons c-h par le palladium." Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13197.
Full textDupont, Jairton. "Activation-fonctionnalisation intramoléculaire de liaisons C-H par le palladium." Grenoble 2 : ANRT, 1988. http://catalogue.bnf.fr/ark:/12148/cb376133600.
Full textRenaudat, Alice. "Fonctionnalisation de liaisons C(sp3)-H non activées catalysées par le palladium." Phd thesis, Université Claude Bernard - Lyon I, 2010. http://tel.archives-ouvertes.fr/tel-00704011.
Full textThiery, Emilie. "Catalyse au palladium : réactions dans l’eau et fonctionnalisation de liaisons C-H." Reims, 2008. http://www.theses.fr/2008REIMS009.
Full textThe work is focused on sustainable chemistry, following three principles of green chemistry: catalysis, safe solvents and prevention of wastes. Recyclable palladium nanoparticles,stabilized by ammonium salts, have been used for the chemoselective hydrogenation of alkenes and the hydrogenolysis of benzylic epoxides in water. The mechanism of alkoxyhydroxylation of allylphenols in aqueous medium has been studied and the different steps of this domino reaction have been proposed. The study of coupling of allylbenzene and 2-methylfuran through C-H activation has shown a competition between the formation of difurylalkanes and furylakenes. The synthesis of difurylalkanes has been developped with various alkenes and the mechanism study has led to propose a catalytic cycle, from which four intermediates have been determined by ESI-MS anaysis. Finally, a preliminary study of allylic oxidation of terminal alkenes has been performed
Goutierre, Anne-Sophie. "Fonctionnalisation C(sp3)-H intermoléculaire par catalyse au palladium : étude de couplages migratoires." Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10220.
Full textThe direct functionalization of C-H bonds is one of the most attractive research subjects today because it constitutes an atom- and step-economical alternative to more traditional synthetic methods. In spite of the significant challenges due to the low reactivity of C-H bonds and their abundance in organic molecules, homogeneous transition metal catalysis has emerged as a powerful tool for their selective transformation. The palladium-catalyzed β-arylation of esters, recently developed in our group, takes advantage of the weakness of the C-H bond α to this group to generate a palladium enolate. The latter can be engaged into a migrative pathway, giving rise to the desired product with a selectivity depending on the aryl bromide and the ligand. The work detailed within this manuscript describes an extension of this methodology to amino esters, which gives rise in only two steps from simple benzylated alanine to a broad range of phenylalanine analogues and useful intermediates to bioactive natural molecules. Following this work, developments of this reaction have led us to consider α-bromo carbonyls as precursors of palladium enolates, leading to the formation of α,β-unsaturated species than can undergo (1,4)-addition reactions. Then, in order to better understand the limitations of our reaction, we have investigated the role of the phosphine ligand by isolating Pd complexes which model key intermediates of the catalytic cycle. Finally, running away from carbonyl compounds, migrative couplings have been explored through a Negishi-type arylation between aryl bromides and alkylzinc species, generated by zinc insertion into alkyl bromides. This reaction gives a very good selectivity in favor of the linear product and can be applied to numerous aryls, but is unfortunately limited so far to a small number of alkylzinc compounds
Ritleng, Vincent. "Fonctionnalisation sélective de liaisons C-H dans des conditions douces : formation de liaisons C-C induites par le ruthénium." Université Louis Pasteur (Strasbourg) (1971-2008), 2001. http://www.theses.fr/2001STR13101.
Full textRoger, Julien. "Arylations d’hétéroarènes via activation / fonctionnalisation de liaisons C-H par des catalyseurs du palladium." Rennes 1, 2010. http://www.theses.fr/2010REN1S086.
Full textDuring this thesis, we are interested in the activation/functionalisation of C-H bonds for the formation of biaryls, which would provide a cost effective and environmentally attractive procedure in comparison to other types of couplings such as Suzuki, Stille or Negishi. First, we demonstrated that it is possible to use electron-rich aryl triflates to functionalize heteroarenes. The best catalytic system seems to be Pd(OAc)₂/PPh₃ with KOAc orCs₂CO₃ in DMF. Then, we have demonstrated that by using as little as 0,1–0,001 mol% of Pd(OAc)2 as the catalyst precursor, without ligand, it was possible to perform a regioselective intermolecular 5-arylation of heteroaromatics such as furans, thiophenes, thiazoles, pyrroles or imidazoles in the presence of aryl bromides. A wide range of substituents, such as acetyl, benzoyl, nitro, nitrile, trifluoromethyl, fluoro, alkyl or methoxy on the aryl bromide are tolerated. In addition, we also showed that it was possible to use of heteroaromatics bearing unprotected amine or alcohol functions. Finally, we have demonstrated that carbonates, which are considered as "green" solvents, can be used for the direct arylation of heteroaromatics. In the presence of propylene carbonate or diethyl carbonate and 1 mol% of PdCl(C₃H₅)(dppb) as the catalyst precursor, it was possible to obtain the 2-arylation of benzoxazole
Vasseur, Alexandre. "Fonctionnalisation C-H d’hétérocycles dérivés de la biomasse : réactions pallado-catalysées de Heck déshydrogénantes." Thesis, Reims, 2012. http://www.theses.fr/2012REIMS017/document.
Full textThis thesis describes Pd-catalyzed dehydrogenative Heck reactions of heteroarenes that could be derived from the biomass with electron-rich alkenes such as styrenes. The first chapter presents a new methodology enabling cross coupling dehydrogenative Heck Reactions of furans and thiophenes with styrenes under Mild conditions and discusses the Influence of the oxidizing agent on the reaction rate. The second chapter focuses on ESI-MS studies of the dehydrogenative Heck reactions of furans with acrylates using benzoquinone as reoxidant and DMSO as solvent. The presentation of a new methodology for aerobic dehydrogenative Heck reactions of heterocycles with styrenes and the explanation about the negative effect of metallic co-oxidants represent the third chapter
Quint, Valentin. "Formation de liaison C-P par fonctionnalisation de liaison C-H sans métal de transition : aspects snthétiques et mécanistiques." Thesis, Normandie, 2017. http://www.theses.fr/2017NORMC219/document.
Full textThis thesis describes the successful development of three modes of activation for the formation of Carbon–Phosphorus bonds under mild conditions and without the use of transition metals.First, a regioselective phosphorylation of pyridines has been developed via a sequential process consisting of the activation of the pyridine with a Lewis acid (BF3) followed by oxidative aromatization mediated by chloranil. The characterization of the Meisenheimer complex enabled to confirm the proposed reaction mechanism. Next, we developed a straightforward approach for the synthesis of benzo[b]phospholes from the reaction of secondary phosphine oxides and alkynes in the presence of an organic oxidant and eosin Y as a catalyst. Apart from the broad scope of this reaction, extensive mechanistic investigations, including EPR, NMR, steady state photolysis permitted the elucidation of the mechanism of this photoreaction. It has been suggested that the oxidant and the photocatalyst come together to form a ground state charge transfer complex that is the driving force of the photocatalyzed process. Finally, we developed a metal-free photoinduced approach for the phosphorylation of anilines and related structures. The reaction proceeded through the formation of an electron donor acceptor complexes between anilines derivatives (electron donors) and N–ethoxypyridinium (electron acceptor). Scope and limitations of this process are discussed along with detailed mechanistic studies
Huang, Qi. "Application of Xanthates to the Synthesis of Azaindanes and to the C-H Functionalization of Heteroaromatics." Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLX114/document.
Full textIn this thesis, we have undertaken an adventure to discover wider application of xanthate chemistry in the construction of fused cycles and direct alkylation of heteroarenes. In Chapter II, we have tackled the problem of preparation of azaindane by taking advantage of the ability of xanthates to mediate both intermolecular addition and intramolecular cyclisation. In Chapter III, an unprecedented investigation into the direct functionalization of pyrazines was described, leading to highly functionalized pyrazines in good yields and good regioselectivity. Finally, in Chapter IV, we have developed a method for the methylation and fluoromethylation of heteroarenes
Barde, Etienne. "Catalyse au cobalt : applications en couplages croisés et en activation/fonctionnalisation de liaison C-H." Thesis, Paris Sciences et Lettres (ComUE), 2018. http://www.theses.fr/2018PSLET019.
Full textOrganic synthesis has been making outstanding recent progress because of the use of transition-metal catalysis into laboratory routine. Among different metals involved in catalysis, cobalt is interesting because of its low cost and toxicity but also because of its unique reactivity.During this thesis, cross-coupling and C—H bond activation reactions using cobalt complexes as catalysts were investigated.A simple catalytic system composed of diphosphine ligand and a cost-effective cobalt salt allowed us to functionnalize α-haloamides using Grignard reagents. A large variety of amides and Grignard reagents (aryl-, vinyl-, alkynyl-) were successfully tested, generating an interesting library of α-functionnalized amides.Moreover, simple cobalt salts were engaged in the activation of the C—H bond of benzamides for the aminoarylation of alkylidene cyclopropanes. Under mild conditions, original and polycyclic molecules were obtained in a single step.These results obtained in two different domains treated in this thesis demonstrate the high potential of simple cobalt salt in catalysis
Raynal, Matthieu. "Nouvelles classes de ligands et complexes métalliques pour la fonctionnalisation d’alcanes par activation C-H." Strasbourg, 2009. https://publication-theses.unistra.fr/restreint/theses_doctorat/2009/RAYNAL_Matthieu_2009.pdf.
Full textHighly active homogeneous catalysts for the dehydrogenation of linear and cyclic alkanes have been developed since 1996. These iridium complexes contained a tridentate bis(phosphine) [for {IrPCP}, A] or bis(phosphinite) ligand [for {IrPOCOP}, B] (Scheme 1). The goal of this work was to synthesize and characterize Nheterocyclic carbenes (NHC) analogues of these complexes (target molecules C, Scheme 1) and to evaluate their activity in alkane dehydrogenation reactions. The transformation of alkanes into alkenes represents a very important reaction, both scientifically and economically. Nheterocyclic carbenes were chosen for their unique stereroelectronic properties. Indeed, NHCs are even better σdonors than trialkylphosphines and can strongly stabilize metal ions. Thus, the dissociation energy of the MNHC bond is particularly high. The features of NHC ligands are important for catalytic applications: the presence of NHC ligands in the coordination sphere of the metal increases the electron density around the metal center. This facilitates the oxidative addition process which is a key step in numerous catalytic systems and notably in the functionalization of alkanes. The fact that the MNHC bond is strong limits the loss of ligand during the catalytic process. In {IrPCP} and {IrPOCOP} complexes, the ligand acts as a « pincer » for the metal. Pincer ligands are rigid, chelating ligands which strongly stabilize metal ions. The resulting homogeneous complexes are thermostable and can be used at relatively high temperatures (200 250°C for {IrPCP} « pincer » complexes for example) without degradation. Metal complexes with pincer, planar and rigid ligands which incorporate at least one NHC functionality have been intensively studied during the last ten years and exhibit unique catalytic properties. However, at the beginning of this project, no NHC pincer complex of iridium was reported in the literature. We have developed a synthetic route towards new hydrido, Nheterocyclic dicarbene iridium(III) pincer complexes (Scheme 2, molecules 12). Hollis et al reported the preparation of the iodidebridged dimer CNHCCCNHC iridium complex 3 (Scheme 2) in 2 steps with a yield inferior to 50%. Our method provides a more direct route and allows the synthesis of the expected complexes 12 in one step from the corresponding bis(imidazolium) salts in almost 70% yield. The diiodide analogues 46 were also isolated in almost 30% yield (Scheme 2). Experimental conditions used to prepare complexes 12 and 46 were thoroughly investigated. The influence of several parameters [nature of the bis(imidazolium) precursor, nature and amount of base, temperature, addition of KI and reaction time] on the course of the formation of NHC complexes and on the nature of the complexes was demonstrated. Reaction intermediates in the synthesis of pincer complexes were isolated and a possible mechanism for their formation was suggested. The NHC dicarbene ligand 7, remarkably stable at room temperature, was prepared and its reaction towards several iridium precursors yielded monoand dinuclear iridium complexes in which the ligand acts as a bridge and no as a chelate or a pincer as might have been anticipated (Scheme 3). The heterodinuclear Ir(I)Rh(I) complex 8, which constitutes a rare example of heterobimetallic complex with a NHC ligand, was synthesized in two steps from 7. The unprecedented and unexpected structure of 9, which possesses a remarkable figure ofeight topology,is useful in order to reconsider some chelate structures postulated in the literature for similar complexes (Scheme 3). Only a few comparative studies dealing with the influence of the nature of the weak base on the course of the formation of NHC complexes have been disclosed in the literature. We were able to demonstrate that higher yields of monoand dinuclear NHC complexes were obtained, for a given reaction time, when Cs2CO3 was used in place of NEt3. For the synthesis of the dinuclear complexes 9, the choice of the base is even more critical, because products are formed only when Cs2CO3 is used. Two different pathways are conceivable for the formation of the IrNHC bond in our complexes: either a combined oxidative addition/HX base assisted elimination process or the formation of the free carbene and its in situ coordination to the Ir(I) center. In the latter case, the higher intrinsic basicity of Cs2CO3 compared to NEt3 would represent an advantage for the generation of a free carbene. Moreover, protonation of the free carbene by the conjugate acid of Cs2CO3 is less likely than the reaction between free carbene and [HNEt3]+X. As mentioned above, we envisaged to use our iridium pincer complexes as catalysts for the functionalization of alkanes. Firstly, we calibrated our experimental conditions with a precursor of reference {IrPOCOP}. Then, we tested 12 and 46, under different conditions, but no significant activity was observed for the transfer dehydrogenation of cyclooctane with tertbutylethylene as olefin acceptor. Several pathways were envisaged to obtain an active catalyst. We are focusing on the synthesis of CNHCCCNHC 16electron iridium(III) pincer complexes (in contrast to 18electron complexes 12 and 46). We are currently studying in the laboratory: (a) the preparation of a complex D (Scheme 4) containing a mixeddonor phosphorus NHC ligand in which the phosphorus substituents can provide the steric hindrance necessary to stabilize a 16electron iridium(III) complex,(b) the increase of the steric hindrance of the NHC ligand by replacing, for example, the nbutyl group by adamantyl groups on the nitrogen of the imidazole rings (E, Scheme 4). Finally, the perspectives of this work include the use of our IrNHC complexes as catalysts for other reactions such as the hydrogenation of trisubstituted alkenes,transfer hydrogenationsor the Oppenauertype oxidationof alcohols. Modifications of the ligand architecture can lead to envisage applications of our complexes in asymmetric catalysis (hydrogenation, transfer hydrogenation or hydrosilylation). RhNHC complexes (hydroformylation or hydroaminomethylation of alkenes) or CrNHC complexes (ethylene oligomerisation) can also find outstanding applications
Lavrard-Meyer, Hubert. "Synthèse et fonctionnalisation du motif pyridine-[b]-bicyclique." Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1186/document.
Full textBicyclic unsaturated structures containing one or more nitrogen atom appear in a widerange of organic compounds. In particular, the [b]-fused pyridine is a frequent structural motif,with striking biological activities. However, there is still a lack for general methods, withrespect to the reaction conditions or the scope. In order to override these limitations, a newsynthetic procedure for preparation of the pyridine ring starting from ß–aminoacrylonitrile isproposed. This procedure relies on a trichloromethyl-activated alkene.The reactivity of pyrazolo[3,4-b]pyridine, a subclass of [b]-fused pyridine, have beeninvestigated. Some late-stage functionnalization have been developped, relying on palladiumcatalyzed chemistry. Three positions of the pyrazolopyridine core have been arylated, thusgiving access to new structures
Piou, Tiffany. "Développement de nouvelles réactions domino impliquant une étape de fonctionnalisation C-H pour la synthèse d'hétérocycles." Thesis, Paris 11, 2012. http://www.theses.fr/2012PA112424.
Full textThe projet consists in developing new domino processes involving C-H functionalization as the key steps. The introduction of C-H functionalization in the domino reaction leads to the enhancing significantly the efficiency of the reaction and offers new perspectives in a synthetic point of view. In this context, we have exploited different strategies basing on Heck/C-H functionalization process, difunctinalization of alkenes reactions through oxidative addition and a sequencial intramolecular aminopalladation/C-H functionalization. These methodologies allow rapid constructions of spiroquinolines, spirooxindoles, 3,3'-disubstituted oxindoles, tetracyclic oxindoles and pyrrolo[1,2-a]indoles cores
Hitce, Julien. "Fonctionnalisation intramoléculaire de liaisons C(sp3)-H catalysée par le palladium : études méthodologiques et applications en synthèse organique." Paris 11, 2007. http://www.theses.fr/2007PA112192.
Full textA palladium-catalyzed intramolecular C(sp3)-H functionalization reaction of benzylic alkyl groups was studied. Both methodological and synthetic aspects were investigated. Thus, in order to determine the scope and the limitations of this new methodology and to emphasize its synthetic value, the reactivity of a variety of substrates was studied using a specifically designed catalyst. This transformation afforded either olefins adjacent to a quaternary carbon atom by dehydrogenation or polycycles by intramolecular arylation of C(sp3)-H bonds. The dehydrogenation methodology was illustrated in the synthesis of the antihypertensive drug verapamil. The mechanism of the new reaction involves 5- and 6-membered palladacycles: the C-H bond cleavage is an intramolecular process. Moreover, the catalytically active species is most probably a molecular complex though the formation of palladium nanoparticles was evidenced. Finally, selective palladium-catalyzed cascade reactions were designed. They combined C(sp3)-H functionalization, Heck cyclization, Heck arylation or olefin hydrogenation to afford valuable 4- and 5-membered carbocycles
Machet, Corinne. "Première approche de la carbonylation directe de la liaison C-H catalysée par des systèmes hétérobimétalliques." Toulouse, INPT, 1990. http://www.theses.fr/1990INPT028G.
Full textBoultadakis, Arapinis Mélissa. "Fonctionnalisation de la liaison C-H anomérique des sucres par insertion de carbène : Un nouvel accès aux cétopyranosides." Thesis, Paris 5, 2012. http://www.theses.fr/2012PA05P640/document.
Full textDue to the major roles of carbohydrates in numerous physiopathological processes, it is essential to develop new chemical tools for glycobiology. A new approach, consisting in the selective functionalization of the anomeric C-H bond of carbohydrates by insertion of a metal-carbene, has been developed, thus offering a new access toward α- and β-ketopyranosides. This is based on the use of a key bromoacetate grafted at position 2 of the sugar, which is the corner stone of a stereoselective glycosylation/diazotransfer/functionalization sequence. Indeed, this group firstly controls the stereoselctivity of the glycosylation step by anchimeric assistance; then, it allows the convenient installation of the carbene precursor to promote quaternarization of the anomeric position. The validation of the concept on model methyl-glycosides has allowed its application on disaccharides. In addition, the sequence has shown good tolerance toward many protecting groups commonly used in carbohydrate chemistry. On the basis of mechanistic studies involving deuterium labeled substrates and DFT calculations, we have shown that this functionalization step follows a concerted or stepwise process depending on the equatorial or axial orientation of the anomeric C-H bond, respectively
Zhang, Zhuan. "Late Stage Modifications of Phosphines using Transition-Metal-Catalyzed C–H Bond Functionalization." Thesis, Rennes, Ecole nationale supérieure de chimie, 2020. http://www.theses.fr/2020ENCR0067.
Full textThe main objective of this PhD thesis deals with the preparation of polyfunctional phosphines by late-stage diversification of commercially available ligands. We have developed rhodium(I)-catalyzed ortho’- C–H bond alkylation of biarylphosphines. This new methodology provides a straightforward access to a large library of multifunctionalized phosphines. Some of these modified ligands outperformed commercially available phosphines in the Pd-catalyzed carboxylation of aryl bromides with carbon dioxide in the presence of a photoredox catalyst. To improve the diversity of biarylphosphines, we have also perfected the P(III)-directed C−H bond alkenylation of (dialkyl)- and (diaryl)biarylphosphines using internal alkynes. Chloride-free [Rh(OAc)(COD)]2 acts as a better catalyst than [RhCl(COD)]2. Conditions were developed to control the mono- and difunctionalization. One of these novel bisalkenylated (dialkyl)biarylphosphines was employed for the preparation of a palladium(II) complex, and some of these functionalized ligands outperformed their corresponding unfunctionalized phosphines in Pd-catalyzed amidation of sterically hindered aryl chlorides. Finally, we have also explored a novel protocol C–H bond alkylation of phosphines via 5- or 7- membered ring cyclometallated phosphineruthenium intermediates. These functionalized phosphines have potential to improve crosscoupling reactions of sterically hindered aryl (pseudo)halides
Tran, Lâm Quang. "Développement de nouvelles réactions dominos catalysées par les métaux de transition impliquant une étape de fonctionnalisation C-H." Thesis, Université Paris-Saclay (ComUE), 2015. http://www.theses.fr/2015SACLS173.
Full textThe direct functionalization of C-H bonds experiencing exponential growth for the past decade. Catalyzed by transition metals, these changes offer an advantage in terms of "green chemistry" and since they allow diversity to overcome the pre-functionalization of the bond to be modified and thus work from simple precursors. Associated with domino process, these reactions often provide efficient access to many heterocycles. It is in this context that fit my thesis work consisting of the development of domino reactions catalyzed by transition metals to design nitrogen heterocycles. We have developed a method which, by choosing wisely precursors, allow a cyclization, catalyzed copper still, giving access to benzimidazole compounds or quinazoline by functionalization C-H. Finally, by integrating the presence of a nitrile function in the multi-component copper catalyzed reaction, we develop an alternative post-cyclization to lead to the formation of quinazolin-2,4-diamine, dihydro-2-amine or benzimidazoquinazoline. In this approach the methodology allows the formation up to 4 chemical bonds through the use of a single catalyst. We have therefore developed a multi-component reaction to access differents structures from a simple methodology, economic cost
Aspin, Samuel. "Arylation migratoire C(sp3)-H d'énolates d'esters." Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10298.
Full textThe transition metal catalysed functionalization of C(sp3)-H bonds unlocks numerous perspectives within organic synthesis in terms of atom economical access routes to otherwise difficult to synthesise molecules. One efficient method to exact such transformations involves the exploitation of an activated C-H bond situated adjacent to an activating electron withdrawing group, allowing facile insertion of a transition metal catalyst species and subsequent functionalization with a new species (normally an aryl group). This strategy is generally termed ‘α-functionalization’. The work detailed within this manuscript describes a diversion from the classic, and well documented α-functionalization reaction, in which rearrangement steps within the catalytic cycle give rise to β- and more remote substrate functionalization. The first new methodology to be described involves a fundamental extension to the in-house developed β-arylation reaction, in which, through careful substrate and ligand choice, this methodology could be applied to achieve the functionalization of simple ester enolates in remote γ- to η - positions. The developed strategy allowed the synthesis of a small range of interesting homophenylalanine analogues, and higher homologues. The second methodology to be described involves a necessary modified protocol for the β-arylation reaction, in which silyl ketene acetals were exploited as mild metal-enolate surrogates, allowing the coupling of base-sensitive substrates. The previously described reaction scope has been extended in terms of both the electrophile and nucleophile coupling partners through the development of mild reaction conditions, which subsequently allowed application of several products towards the synthesis of lactones
Millet, Anthony. "Alpha-, beta-, gamma-fonctionnalisation sélective de N-Boc-amines : extension du couplage migratoire palladocatalysé." Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10269.
Full textSince several years, the emergence of terms such as atom- and step-economy, or the need for the development of rapid and efficient synthetic methods have taken an important place in chemistry. In this context, the transition-metal-catalyzed functionalization of unactivated carbonhydrogen bonds has emerged as a powerful tool and an important field of research. In 2010, the development of the β arylation of esters has initiated a new perspective in our laboratory, and has been at the origin of the research described in this manuscript on the selective C(sp3)–H functionalization of amines at α, β and γ positions. The work performed during this Ph.D. project is related to the Negishi cross-coupling reaction (co-laureate of Chemistry Nobel prize in 2010), an important method for the formation of carbon-carbon bonds. Three different aspects are explored in this manuscript. The first one deals with the development of the palladium-catalyzed β -arylation of N-Boc-piperidines, which highlights the importance of ligand flexibility to control the α- vs. β- arylation selectivity. The second part focuses on the selective α - and β -functionalization of acyclic N-Boc-amines, which required to reinvestigate the directed lithiation of acyclic amines and to synthesize new biarylphosphines possessing greater flexibility. A kinetic analysis of each individual step from the lithiation to the α -arylation was performed by in situ IR spectroscopy, and proved an efficient method to gain further mechanistic insights. Finally, we have developed a selective γ - arylation reaction of allylamines, which represents a new extension of the Negishi cross-coupling for the C–H functionalization of alkylamines, and allows a direct access to valuable γ -arylamines and β - arylaldehydes
Pierre, Cathleen. "Synthèses de molécules polycycliques par arylation C(sp³)-H intramoléculaire catalysée par le palladium." Phd thesis, Université Claude Bernard - Lyon I, 2012. http://tel.archives-ouvertes.fr/tel-00975446.
Full textSmari, Imen. "Synthèse et réactivité en catalyse de nouveaux hétéroaromatiques." Thesis, Rennes 1, 2016. http://www.theses.fr/2016REN1S012/document.
Full textThis thesis work dealing with the activation / functionalization of CH bonds for the formation of derivatives of heteroaryl. We sum so interested in the reactivity of derivatives of 4-formylpyrazole for pallado-catalyzed via CH bond activation couplings. The formyl C4 is used to control the regioselectivity of the arylation. Subsequently, we investigated the reactivity of 2-bromofluorènes in these coupling reactions. The third part focuses on the synthesis of aminothiophenes and pyrrolyl-thiophene. The originality of our approach is the use of these compounds as a precursor in pallado-catalyzed reactions. Finally, the last part is devoted to the reactivity of 3-bromobenzothiophene in pallado-catalysed reactions without cleavage of the C-Br bond C3 benzothiophene
Pialat, Amélie. "Formation de liaisons C-N et C-O par catalyse de coordination ou par oxydation à l'iode hypervalent." Thesis, Montpellier 2, 2013. http://www.theses.fr/2013MON20204/document.
Full textThe direct functionalization of C-H bonds offers an attractive, atom- and step-economical alternative to traditional methods based on functional group transformations. Intermolecular C(sp3)-H amination reactions involving nitrene intermediates usually proceed with moderate yields and regioselectivities. In this context, new bifunctional compounds were developed and applied to copper and silver-catalyzed C-N bond-forming reactions. These systems, however, have been found to be ineffective under the reaction conditions.Our research has also focused on the iodine(III)-mediated nucleophilic functionalization of anilides. The direct triflation and triflimidation of acetanilides were accomplished with the use of affordable and easy-to-handle silver(I) triflate or triflimidate respectively, under mild oxidative conditions, exhibiting perfect regioselectivity for the para position. A complete optimization of the reaction conditions and an evaluation of the scope allowed us to prepare a variety of diversely substituted aryltriflates (and nonaflates) in synthetically useful yields
Sundararaju, Basker. "Cyclisation de dérivés de β-amino acides par métathèse et nouveaux catalyseurs pour l'allylation regiosélective et la fonctionnalisation C-H." Rennes 1, 2011. http://www.theses.fr/2011REN1S148.
Full textAu cours de cette thèse, de nouveaux complexes du ruthénium ont été évalués dans trois différentes applications. Des complexes inédits Cp*Ru(IV) ont été préparés et ont permis de réaliser des réactions d'allylation régiosélectives en faveur des dérivés ramifiés à partir de divers dérivés allyliques, et plus particulièrement directement à partir d'alcools allyliques sans groupement partant. L'incorporation en des positions choisies de motifs allyliques à des dérivés de β-aminoacides a été réalisée grâce à l'utilisation de catalyseurs de type [RuCp*]. Leur cylcisation en présence de catalyseur de métathèse ruthénium alkylidène a permis l'accès à divers mono-, di- et tétra-peptides incorporant des structures cycliques de taille moyenne et macrocycliques. Enfin, des complexes originaux du ruthénium (p-cymène)(II) ont été préparés. . Ils ont été engagés avec succès dans des réactions de transfert d'hydrogène et permis l'alkylation d'amines cycliques avec de bons rendements, et de façon plus importante, l'alkylation régiosélective en C(3) des mêmes amines
Rodrigues, Alves Romain. "Approches synthétiques vers la pactamycine et les raputindoles. Hétérocycles azotés par réaction multicomposant." Thesis, Université Paris-Saclay (ComUE), 2018. http://www.theses.fr/2018SACLS062/document.
Full textThe search for small bioactive molecules and molecular diversity are constant sources of inspiration for organic chemists. In this context, major developments in the design of always more effective, flexible and environment-friendly synthetic methods were described, in particular thanks to organometallic catalysis. Within this context, this Thesis project deals with the development of synthetic approaches towards natural molecules or simplified analogues, and the development of a new methodologies for the synthesis of nitrogen-containing heteroaromatic compounds.The first part of this manuscript concerns the development of a synthetic strategy towards a cyclopentitol platform, found in the natural products pactamycin and jogyamycin which show a great pharmacological potential. This project involves the use of catalytic nitrene transfers within aziridination and C-H amination reactions.The second part of the project describes a total synthesis approach towards a new class of natural products, the raputindoles. The key step is a [3+2] cycloaddition reaction, catalysed by an iridium complex, to prepare indanes possessing two asymmetric centres whose stereochemistry can be controlled. Finally, the third part is devoted to the development of a domino multicomponent reaction, catalysed by copper, for the synthesis of heteroaromatic compounds. Quinazolin-4(3H)-imines, quinazolin-4-ones and benzimidazo[1,2-c]quinazolines can be obtained from the same catalytic system, by the assembly of a cynamide, a boronic acid and an amine with an unique catalytic system
Sofack-Kreutzer, Julien. "Synthèses de carbocycles et d'hétérocycles à cinq chaînons par activation de liaisons c(sp3)-h non activées." Phd thesis, Université Claude Bernard - Lyon I, 2011. http://tel.archives-ouvertes.fr/tel-00744243.
Full textHezard, Nathalie. "Bilan de notre experience du diagnostic antenatal de la toxoplasmose congenitale au c. H. R. U. De reims de 1987 a 1993." Reims, 1994. http://www.theses.fr/1994REIMM035.
Full textCavaillé, Anthony. "Complexes de fer à bas degré d'oxydation pour l'activation du diazote atmosphérique, extension aux liaisons C-H et au phosphore blanc." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30338.
Full textMolecular nitrogen activation and functionalization are one of the most challenging topic in modern chemistry. The industrial formation of ammonia by the Haber-Bosch process, essential for current agriculture, is the starting point of this field. Indeed, the strong energetic need of this transformation has motivated academic research to find catalyst that can work in milder conditions as observed with nitrogenase enzymes. The principal goal of this Ph.D. work was the synthesis and the study of low oxidation states iron complexes bearing triphosphine ligand for the catalytic formation of ammonia and silylamines. This experimental work was supported by theoretical calculation using DFT in order to rationalize and understand the different results. The first part of this manuscript presents the metallic precursors synthesis and the first reduction attempts using Grignard reagents. During this part, the formation of an interesting Fe0 bis-dinitrogen complex was observed. Its efficient synthesis and reactivity was studied in a second part. This complex is one of the few homogeneous iron catalysts able to perform the formation of ammonia and one of the most active for N(TMS)3 formation. Furthermore, this Fe0 center is able to dehydrogenate an alkane part of its ligand and activate another small molecule of interest, white phosphorus. This new reaction leads to the firs example of the formation of an end-deck iron cyclo-P4 complex and is the subject of the third part. Finally, several iron complexes bearing dinitrogen and hydride ligand were studied in relevance with the nitrogenase enzyme. This part was an opportunity for a change toward a PCP-type ligand. The carbenic form of this ligand was reachable by double C-H activation at an intermediate Fe0 center
Nasrallah, Ali. "Complexe de Rhodium(II) et iode hypervalent en catalyse : époxydation d’alcènes et amination de liaisons C(sp³)-H." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLS427.
Full textThis thesis describes the development of new catalytic processes by combining hypervalent iodine reagents with rhodium (II) complexes.The first chapter concerns the observation of the epoxide as a unexpected product under catalytic nitrene transfer conditions, and the development of a new method to promote the epoxidation of alkenes by combining a reagent of hypervalent iodine (III) and a complex of dirhodium (II).The second chapter is centered on the development of a general method forasymmetric intermolecular benzylic C(sp³)–H amination by combining a chiral rhodium (II) catalyst and a benzyl sulfamate, and the application of this method on large scale.The third part of this work show the development of a regioselective C(sp³)–H amination of unactivated alkane by rhodium (II) catalysis, using a stoichiometric amount of alkane as the substrate
Boquet, Vincent. "Aziridination énantiosélective et Amination C(sp³)-H chimiosélective catalysées par des complexes de rhodium(II) : développements méthodologiques et application à la fonctionnalisation tardive de produits naturels." Thesis, université Paris-Saclay, 2021. http://www.theses.fr/2021UPASF012.
Full textThis thesis describes the development and application of aziridination and C(sp³)–H amination reactions involving rhodium(II) catalyzed nitrene transfers. In the first chapter, the development of an enantioselective intermolecular alkene aziridination reaction is reported. This reaction is based on the use of sulfamate derived from 4-tert-butylphenol as the nitrene precursor, and a chiral dirhodium(II) complexe derived from tert-leucine. The scope of this transformation and the some synthetic modifications of the enantioenriched aziridines are presented. The second chapter is centered on the development of a catalyst-controlled selective C(sp³)–H amination of tertiary C–H bonds in the presence of benzylic C–H bonds. This peculiar selectivity is obtained with the combinaison of the same reagents used in the first chapter. The scope, involving isobutyl and isoamylbenzene derivatives, and the interest of this new reaction are described. In a second part, the development of a regioselective C(sp³)–H amination of alkanes is described. This method enables the efficient synthesis of tertiary amines by using alkanes as the limiting components. The third part presents the late-stage functionalization of fislatifolic acid derivatives via catalytic nitrene transfer reactions. Application of methods developped in our team has lead to the synthesis of 11 aminated analogues with good yields, selectivities, and interesting biological properties
Lazib, Yanis. "Amination de liaisons C(sp³)–H catalysée par des complexes de rhodium(II) : applications à la synthèse d’hétérocycles azotés et d’une molécule naturelle la crambescin B281." Electronic Thesis or Diss., université Paris-Saclay, 2021. http://www.theses.fr/2021UPASF060.
Full textThis thesis is devoted to the development and application of C(sp³)-H amination reactions by rhodium(II) catalyzed nitrene transfer. The first part describes the application of C(sp³)-H amination reactions for the preparation of pyrrolidines based on the laboratory's expertise in the field of nitrene insertion reactions and on radical reactions of the Hofmann-Löffler-Freytag type. In this respect, an asymmetric intermolecular C-H amination reaction allowed us to install a nitrogen function in a regio- and stereoselective manner within hydrocarbons. This nitrogen has then enabled to drive a second C-H amination reaction via intramolecular hydrogen atom transfer [1,5]. This second fully regioselective step led to pyrrolidine units after cyclization. In the last part, a synthetic route to obtain a natural molecule, crambescin B281, was explored. This work is based on the use of two C(sp³)-H amination reactions catalyzed by rhodium(II) complexes. These two intramolecular amination steps have enabled the introduction of a nitrogen atom with high regio- and diastereoselectivity in order to lead to key intermediates in the synthesis of crambescin B281