Dissertations / Theses on the topic 'Réactif de Grignard'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the top 27 dissertations / theses for your research on the topic 'Réactif de Grignard.'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Browse dissertations / theses on a wide variety of disciplines and organise your bibliography correctly.
Péralez, Eric. "Contribution à la détermination du mécanisme de formation du réactif de Grignard." Aix-Marseille 3, 1996. http://www.theses.fr/1996AIX30092.
Full textBoukattaya, Fatma. "Addition d'organomagnésiens sur des nitriles fonctionnalisés : application à la synthèse de molécules d’intérêt biologique." Thesis, Le Mans, 2016. http://www.theses.fr/2016LEMA1007.
Full textThe nucleophilic addition of Grignard reagents on nitriles generally leads to ketones after acidic hydrolysis. The double addition, providing tertiary carbinamines after work-up, is more difficult and usually occurs only with allylic Grignard reagents. In this context, we discovered that Grignard reagents can perform a double addition on the nitrile function of acyl cyanohydrins, to provide hydroxyamides. This reaction is original by the fact that a wide range of Grignard reagents can be used, in particularly mild conditions. This reaction has been applied to the synthesis of different α,α-disubstituted α-aminoacids, by oxidation of the alcohol functionality and hydrolysis of the amide moiety. Especially, divinylglycine has been prepared in good yield. The successive addition of two different Grignard reagents was also carried out, after optimization of reaction conditions, to access unsymmetrical hydroxyamides, which are precursors of chiral quaternary aminoacids. Finally, the addition of the Grignard reagents on N-ethoxycarbonyl 3-cyano-iminocoumarines was studied. Despite the presence of several electrophilic centers, the reaction is highly chemoselective, and novel chromenes displaying substituent on position 4 were obtained. The antifungal and antibacterial properties of these compounds have been evaluated
Hazimeh, Hassan. "Réactivité des horloges radicalaires aromatiques vis-à-vis du magnésium, du potassium et de l'électron solvaté : transfert d'électron hétérogène versus homogène et mécanisme de formation du réactif de Grignard." Aix-Marseille 3, 2005. http://www.theses.fr/2005AIX30048.
Full textThis thesis investigates the mechanism of formation of aromatic organomagnesium compounds. We prepared a set of new radical clocks. Experiments with magnesium show that aryl radicals are formed. We showed that root of the selectivity between linear and cyclized Grignard reagents is highly dependent upon the zone where radicals are formed. The phenyl group present in our radical clocks could play an original role of mediator. Experiments with potassium and solvated electron reveal a dramatic difference between heterogeneous and homogeneous electron transfer : percentages of cyclised products diminish strongly in heterogeneous medium. The main cause of this contrasting behaviour could be the higher reducing efficiency of the metallic surface. We propose a new mechanism based on the electrochemical model developped by Savéant and Amatore (kinetic zone approach). This approach brings a fresh view about the root of selectivity during the formation of aromatic Grignard reagents
Caillé, Julien. "Réactivité d’organométalliques sur des nitriles fonctionnalisés : réactions de cyclopropanation asymétrique et double addition." Thesis, Le Mans, 2017. http://www.theses.fr/2017LEMA1028.
Full textCyclopropylamines are important scaffolds in medicinal chemistry. Among the syntheses of the aminocyclopropane moiety, the Kulinkovich-related reactions applied to amides and nitriles furnish straightforward access. However, no efficient asymmetric version has been published to date. In a first part, the study of optically active titanium complexes for the preparation of chiral spirolactams from cyanoesters has been undertaken. This work allowed us to setup a quick evaluation method for chiral ligands whose screening revealed that Taddol and its derivatives lead to the best enantiomeric excesses. However, the enantioselectivity remains too low for synthetic purposes. In a second part, the synthesis of tertiary carbinamines, another important scaffold, has been studied from acylcyanohydrins and organometallics. Notably, the synthesis of a quaternary aminoacids library was achieved. The incorporation of two different organometallics on acylcyanohydrins was also undertaken, leading to the preparation of chiral hydroxyamides in a racemic fashion. Lastly, very good yields in double addition products were obtained by using allylic organozinc reagents. The obtained hydroxyamides were used as precursors of polyfunctional linkers for the chemical ligation
Barré, Baptiste. "Fonctionnalisation d'hétérocycles par des réactions métallo-catalysées." Thesis, Paris 6, 2016. http://www.theses.fr/2016PA066461.
Full textCross-coupling reactions, as Prof. K. C. Nicolaou said “have changed the way we think about synthesis”. Indeed, cross-coupling reactions are powerful tools to access easily and rapidly to a library of compounds in the context of medicinal chemistry. Palladium-catalysed cross-coupling rules the field and was recognized by the Nobel Prize in 2010 but, since its discovery, others metals have appeared as good alternatives to the expensive and toxic palladium salts such as copper, nickel, cobalt and iron salts. In medicinal chemistry, heterocycles are essential moieties since they are found in a great number of drugs on the market. It is always a challenge for organic chemists to develop new methods to produce motifs with interesting pharmacological properties such as substituted azetidines, pyrrolidines and oxetanes. sp3 Halides are challenging substrates for cross-coupling because the oxidative addition of the metal in the C-X bond is difficult and because side reactions can take place like -hydride elimination or dehydrohalogenation. Nevertheless, cobalt and iron are suitable catalysts to perform cross-coupling reactions on sp3 halides. Herein, we would like to report two catalytic systems allowing the cross-coupling between heterocyclic alkyl halides and Grignard reagents using cobalt and iron salts. A mechanistic study on cobalt-catalysed cross-coupling reaction between halides and Grignard reagents will be also presented
Ben, Hassen Samia. "Electrodéposition du magnésium à partir des solutions à base de réactifs de Grignard et tenue à la corrosion du revêtement formé." Besançon, 2009. http://www.theses.fr/2009BESA2037.
Full textMagnesium deposits were applied as cathodic coatings to protect steel against corrosion. These magnesium deposits were obtained by electrodeposition with direct current method from six different Grignard solutions in their appropriate solvents. Ln aggressive chloride solutions, the best corrosion protection efficiency was obtained with magnesium deposit electroplated from methylmagnesium chloride solution in tetrahydrofurane. The use of pulsed current method improved remarkably the morphology and the texture of the magnesium deposit and consequently the corrosion protection efficiency was also enhanced. However this protection efficiency is time limited. In order to improve the time life of the magnesium coating, cerium treatments were applied. The obtained cerium conversion layer was mainly composed by ceria CeO2 which reinforced the corrosion protection by a barrier mechanism. In this work, electrochemical and analytical analyses were assumed with these following techniques: open circuit potential, polarization curves, EIS, SEM, EDS, XRD, FTIR and SDL
Aissaoui, Regadia. "Réaction de substitution nucléophile aromatique des acides naphtoïques ortho-fluorés/méthoxylés avec les réactifs de Grignards et les organolithiens (SNArAB)." Phd thesis, Université du Maine, 2012. http://tel.archives-ouvertes.fr/tel-00684960.
Full textYoussefi, Mohammad. "Recherche de nouvelles synthèses de sélénophosphonates : Préparation et étude de la réactivité d'ène-phosphoramides fonctionnels." Nancy 1, 1986. http://www.theses.fr/1986NAN10105.
Full textBoutahir, Driss. "Étude théorique de la structure et de la réactivité des réactifs de Grignard." Nancy 1, 1992. http://www.theses.fr/1992NAN10054.
Full textAndersen, Claire. "Catalyse au cobalt et au cuivre : Couplages croisés entre des (pseudo)halogénures d'alkyle et des réactifs de Grignard." Thesis, Paris Sciences et Lettres (ComUE), 2019. http://www.theses.fr/2019PSLET048.
Full textMost of the marketed drugs contain one or more aromatic rings in their structure. Even though, those moieties are often essential for a molecule to interact with its target, a too high number of aromatic rings can have a negative impact on the physico-chemical properties and on the toxicity of a drug candidate. It is therefore of high interest to replace a phenyl ring by bioisosteres, such as strained cycles (cyclopropane, cyclobutane, bicyclo[1.1.1]pentane). During the course of this thesis, two methods have been developed for the cross-coupling of alkyl (pseudo)-halides with several Grignard reagents containing strained cycles. The first method relies on a cobalt catalytic system and allow the cross coupling of the cyclopropylmagnesium bromide as well as the cyclobutylmagnesium bromide with alkyl iodides. The cross-coupling has also been extended to the use of alkenyl Grignard reagents. The second method uses a copper salt to achieve the cross-coupling of alkyl (pseudo)-halides with bicyclo[1.1.1]pentane Grignard reagents. Both cross-coupling are robust, easy-to-handle and simple and cheap catalysts are used. As these cross-couplings are chemoselective they are promissing powerful synthetic tools for medicinal chemists
Beaufort, Virginie. "Contribution à la chimie des alpha aminonitriles." Clermont-Ferrand 2, 2005. http://www.theses.fr/2005CLF22557.
Full textEssadiq, Hassan. "Synthèse et structure de nucléosides a désoxysucres ramifiés." Lyon, INSA, 1987. http://www.theses.fr/1987ISAL0011.
Full textHallouis, Sophie. "Etude des associations réactifs de Grignard-borohydrures (Zn, Ca, Li) : réduction et alkylation-réduction de dérivés d'acides." Lyon 1, 1998. http://www.theses.fr/1998LYO10020.
Full textBodineau, Nicolas. "Le magnésium : réduction d'hydrocarbures polyaromatiques et étude du mécanisme de la formation des réactifs de Grignard aromatiques." Aix-Marseille 3, 2000. http://www.theses.fr/2000AIX30078.
Full textAfter more than 70 years of experimental investigations, the mechanism of formation of the Grignard reagent is far from being fully understood. This thesis aims at the semi-quantitative determination of the reducing ability of magnesium under various states (clusters of various size, turnings), and the mechanism of formation of aromatic organomagnesium compounds. The first part deals with the reduction of polyaromatic hydrocarbons of known E° by magnesium. These reductions eventually lead to the formation of radical anions, characterised by ESR spectroscopy. A value of the reduction potential of the couple Mg/̂Mg is estimated, and the Marcus theory is applied to the Grignard reagent formation. On the other hand, this work strongly hints that the reduction potential of Mg°/Mg is dependent upon the type of magnesium (turnings or highly divided magnesium). Quantum size effects are for the first time evidenced for Mgn clusters with small n. The second part is devoted to the inhibition effect in the Grignard reagent formation. .
Lemoucheux, Laurent. "Etude de la synthèse d'amides par couplage de chlorocarbamates et d'organométalliques en vue de son application en chimie du carbone-11." Caen, 2001. http://www.theses.fr/2001CAEN2053.
Full textGAROT, CATHERINE. "Diphosphacyclopropanes - Disphophapropanes : eréarrangements et interconversion." Toulouse 3, 1993. http://www.theses.fr/1993TOU30033.
Full textGaquère-Leprêtre, Anne. "Synthèse et étude d'organométalliques (Li, Zn, Mg, Cu) en série hétérocyclique π-déficitaire (diazines, pyridine). Optimisation par sonication." Rouen, 2000. http://www.theses.fr/2000ROUES012.
Full textBariau, Annabelle. "Synthèse de bétâ-aminocétones optiquement pures." Clermont-Ferrand 2, 2004. http://www.theses.fr/2004CLF21514.
Full textPothion, Catherine. "Etude de la réactivité des N-uréthane-N-carboxyanhydrides d'acides aminés (UNCAs) en chimie des peptides." Montpellier 2, 1997. http://www.theses.fr/1997MON20214.
Full textEjjiyar, Soumeya. "Synthèse stéréosélective et ouverture d'alcools tétrahydrofurfuryliques : applications à la synthèse de diols-1,2 et d'oléfines disubstituées." Lyon 1, 1988. http://www.theses.fr/1988LYO10087.
Full textBakhchinian, Robert. "Synthèse de nouveaux hétérocycles oxygènes à propriétés antistrogènes potentielles : analogues structuraux du tamoxifène." Versailles-St Quentin en Yvelines, 1998. http://www.theses.fr/1998VERS0015.
Full textDíez, González Silvia. "Synthèse d'un modèle des cycles A et B de la 10-silatestostérone." Paris 11, 2004. http://www.theses.fr/2004PA112096.
Full textSince the 60's, different types of organosilicon compounds have shown a great biological activity. Steroids with a silicon atom in the position 6 with two methyl groups on the silicon atom have been reported, but they have not shown any hormonal activity. The substitution of one of the quaternary atoms of carbon of a steroid by a silicon atom should lead to a silasteroid stable enough in a biological environment without introducing any supplementary substituent in comparison to the carbon analogue. We have developed a synthetic route to prepare 1-silabicyclo[4. 4. 0]dec-5-en-4-ones. The enone with a methyl group on the silicon atom is a model of cycles A and B of the 10-silatestosterone. In a first time, six different approaches for preparing 2-methyliden-1-silacyclohexanes with various substituents on the silicon atom have been studied. Two of these approaches have turned to be good synthetic methods for these compounds: whether from polyhalosilanes and the 2,6-dibromohexene under the Barbier or Grignard conditions, or from (hex-5-ynyl)silanes by an intramolecular hydrosilylation. In a second time, we have tackled the preparation of 2-methyliden-1-silacyclohexanes with a 3-oxopropyl chain on the silicon atom. The ene reaction of these aldehydes has led to the formation of silabicydodec-6-en-ols with excellent yields and diastereoselectivities. These silabicyclic alcohols have been transformed into alpha, beta-ethylenic compounds in two steps with good yields
Cavaillé, 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
Dörr, Aurélie. "Synthèse de nouveaux analogues de la phénylalanine." Thesis, 2007. http://hdl.handle.net/1866/17997.
Full textSt-Onge, Miguel. "Synthèse stéréosélective de dérivés pipéridines polysubstitués par fragmentation de Grob." Thèse, 2008. http://hdl.handle.net/1866/3472.
Full textThis thesis discusses the formation of piperidine derivatives using the Grob fragmentation. Firstly, an introduction of the important alkaloid family as well as previous work completed by the Charette group towards the synthesis of these compounds will be demonstrated. This will be followed by a summary of the Grob fragmentation including a discussion of the reaction conditions, molecular structures, stereoelectronic requirements and modifications of the Grob fragmentation. Chapter 2 will be dedicated to the development of the methodology and more precisely, to the optimization of all parameters necessary to the reaction. Furthermore, the scope of the reaction and some explanation of the regioselectivity and the diastereoselectivity of the reaction will be discussed. The developed methodology can be used in a total synthesis and will be demonstrated in Chapter 3. Moreover, using the frangomeric effect concept, a mechanistic study on the Grob fragmentation will be discussed. Finally, some future projects, especially possible improvement of the methodology, will be presented in the last chapter. This is followed by a conclusion and a summary of the work completed on this project.
Iden, Hassan. "1,4-Diazepin-2-one Synthesis." Thèse, 2007. http://hdl.handle.net/1866/7801.
Full textChen, Bin. "Design and synthesis of constrained azacyclic pyrrolidine analogues of FTY720 as anticancer agents & metal coordination-controlled and bifunctional catalysis toward tertiary β-Ketols." Thèse, 2015. http://hdl.handle.net/1866/13959.
Full textThis thesis consists of two parts: Part 1: Design and synthesis of constrained azacyclic pyrrolidine analogues of FTY720 as anticancer agents FTY720 is presently marketed as a drug (GilenyaTM) for the treatment of relapsing-remitting multiple sclerosis. It functions as an immunosuppressant due to its effect on sphingosine-1-phosphate (S1P) receptors. At higher doses, FTY720 also has antineoplastic actions. However, at such doses it induces bradycardia due to the activation of the S1P1 and S1P3 receptors. This limits its potentical to be used as a cancer therapy in humans. Our previous studies have shown that some constrained pyrrolidine analogues of FTY720 have anticancer activity but no activity toward S1P1 and S1P3 receptors. We reasoned that a study of the structure-activity relationships (SARs) could lead to the discovery of new effective antitumor agents. Thus, two series of constrained analogues (O-arylmethyl-substituted pyrrolidines and C-aryl-substituted pyrrolidines) were designed and synthesized (Chapter 1). These analogues showed excellent cytotoxic activity against various human cancer cells (prostate, colon, breast, pancreas and leukemia). Especially, several active analogues, which cannot be phosphorylated by SphK, have the potency to be further studied in the treatment of cancer without inducing bradycardia. Mechanistic studies suggest that these constrained analogues trigger down-regulation of nutrient transporters, which induce a bioenergetic crisis and the cancer cells starve to death. To further investigate their target receptors, we have designed and synthesized diazirine based photo-affinity labeling (PAL) probes (Chapter 2). Aided by the PAL technique, information regarding the target receptor could be obtained through LC/MS/MS protein analysis. These tests are in progress and the preliminary results appear promising. Part 2: Metal coordination-controlled and bifunctional catalysis toward tertiary β-ketols The Barbier and Grignard reactions are classical methods to form carbon-carbon bonds, and generally used to prepare secondary or tertiary alcohols. In an attempt to perform a Grignard reaction with n-butyl iodide under Barbier one-pot conditions, we obtained major product β-hydroxyl ketol from the self-aldol reaction of 5-hexen-2-one, rather than the expected addition alcohol product (Chapter 3). The unusual β-ketol formation was also observed using other methyl ketone substrates. Interestingly, in an intramolecular reaction of a triketone substrate, which is well known to give the Hajos-Parrish ketone, the favored product was a rarely studied β-ketol with the hydroxyl group at axial position. Intrigued by these results, after systematic reaction condition studies, we developed two new methods toward the catalytic synthesis of specific β-ketols by intramolecular cylcization in high yield and selectivity (Chapter 4). The reaction can be catalyzed either by a suitable base and lithium bromide as the additive, through a lithium pre-organized transition state or by a bifunctional catalyst TBD (triazabicyclodecene), through a TBD mediated bidentate transition state. The proposed mechanisms were corroborated by DFT computation. These catalytic reactions were also extended to other triketone and diketone substrates. Although the initial efforts to achieve enantioselectivity were not successful, they merit further study of the synthesis and investigation of new chiral catalysts.