Dissertations / Theses on the topic 'Addition de Michael diastéréosélective'
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Gendron, Thibault. "Synthesis and evaluation of the antiparasitic activity of diarylideneacetones and their related thiopyranone and S-oxide prodrugs." Thesis, Strasbourg, 2012. http://www.theses.fr/2012STRAF064/document.
Full textHuman African trypanosomiasis, Chagas disease and leishmaniasis are parasitic diseases that significantly affect the populations and thus the economy of many developing countries. With the aim of developing new therapeutic agents to cure these diseases, we focused our research on two series: the diarylideneacetone and the 2,6-diaryl-4H-tetrahydrothiopyranone series.To complete and expend preliminary results that had been previously obtained in our laboratory, a generalization and an optimization of the protocols was intended. Thus, a novel Palladium-catalyzed synthesis of (hetero)dissymmetric diarylideneacetones was developed and optimized in collaboration with Prof. T. J. Müller (University of Düsseldorf). In spite of excellent antiparasitic activities, most of the diarylideneacetones were toxic toward human cells.2,6-Diaryl 4H-tetrahydrothiopyranones and their related S-oxides were designed to cope with major toxicity issues. Acting as prodrugs, these molecules are prone to undergo β-elimination of the sulfurated intracyclic group, regenerating the parent diarylideneacetone. The diastereoselective synthesis of this scaffold is not extensively described in the literature. Consequently, novel diastereoselective methodologies have been developed and generalized to a wide panel of substitution patterns. Results of the biological assays demonstrated that sulfide and S-oxide prodrugs displayed a lowered toxicity while the potency was maintained, thus confirming the validity of the prodrug strategy
Toueg, Julie. "Vers la synthèse du tricylce ABC de l'acide hexacyclinique." Phd thesis, Ecole Polytechnique X, 2007. http://pastel.archives-ouvertes.fr/pastel-00003153.
Full textCastelot-Deliencourt, Géraldine. "Synthèse diastéréosélective de composés amidophosphorés : accès à des molécules biologiquement actives et à des ligands pour la catalyse asymétrique." Rouen, 2000. http://www.theses.fr/2000ROUES067.
Full textSantoro, Francesco. "Ruthenium/PNNP-catalyzed asymmetric Michael addition /." Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17024.
Full textPoderi, Cecilia. "Synergistic catalysis: Michael addition of acyl-pyridines." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2017. http://amslaurea.unibo.it/14409/.
Full textRotulo-Sims, Delphine. "Synthèse diastéréosélective de diols-1,3 et de triols-1,3,5 à partir de vinyl sulfones." Palaiseau, Ecole polytechnique, 2005. http://www.theses.fr/2005EPXX0008.
Full textChaumette, Jean-Louis. "Synthèse asymétrique d'acides α-halogénés par halogénation diastéréosélective d'acétals de cétènes silylés ; addition asymétrique d'alcools sur des cétènes α-halogénés." Rouen, 1996. http://www.theses.fr/1996ROUES052.
Full textPelzer, Silke. "Wie es geht eine quantenchemische Untersuchung der eisenkatalysierten Michael-Reaktion /." [S.l.] : [s.n.], 2004. http://deposit.ddb.de/cgi-bin/dokserv?idn=971232482.
Full textSaraiva, rosa Nathalie. "Synthèse diastéréosélective de molécules azotées α-trifluorométhylées - Élaboration et études conformationnelles de petits peptides incorporant des acides β-aminés trifluorométhylés." Thesis, Reims, 2017. http://www.theses.fr/2017REIMS013.
Full textChiral N-tert-butansulfinamides, developped by Ellman 20 years ago, have been increasingly applied for the preparation of chiral functionnalized amines, because of the affordability of both enantiomers and of their mild conditions of cleavage. However, the use of theses auxiliaries for the synthesis of quaternary trifluoromethyl derivatives remains quite limited, the corresponding trifluoromethyl ketoimines being highly unstable.Chiral N-tert-butanesulfinyl alkyl(aryl) trifluoromethyl hemiaminal ethers have been developped to be used as bench-stable surrogates of these ketoimines : once under reaction conditions, they afford the corresponding ketoimine in situ, which can be subject to a nucleophilic addition.In this manuscript, different reactions led on these hemiaminal ethers are described, affording valuable and optically pure trifluoromethylated quaternary building-blocks : on the one hand, homoallylic amines, obtained by the addition of allylalane species, and which can afford, after a few steps, teh corresponding trifluoromethyl azetidines, and on the other hand, chiral trifluoromethyl β3,3-amino acids, afforded by a highly diastereoselective Reformatsky reaction.These β 3,3-amino acids have been then involved in solution-phase peptide couplings in order to synthetise a wide range of α/β- and β-di- and tripeptides, whose conformation have been the object of preliminary studies in the solid state and/or in solution.Key-words : Ellman auxiliary, Nucleophilic addition, Solution-phase peptide coupling, α-trifluoromethylated nitrogen derivative, Hemiaminal ether, asymmetric synthesis
Schmidt, Christian. "Darstellung konformativ eingeschränkter Glutaminsäurederivate durch Michael-Addition von chelatisierten Glycinesterenolaten." [S.l.] : [s.n.], 2007. http://deposit.ddb.de/cgi-bin/dokserv?idn=984726101.
Full textDu, Haiying. "Michael addition-initiated organocatalytic enantioselective multicomponent reactions with 1,3-dicarbonyls." Thesis, Ecole centrale de Marseille, 2014. http://www.theses.fr/2014ECDM0002/document.
Full textThis thesis focuses on the development of enantioselective multicomponent reactions with 1,3-Dicarbonyls in the presence of an organocatalyst, to synthesize fused polyheterocyclic motives.At first, we describe our initial results on an enantioselective multicomponent reaction with enals and simple primary amines. In view of the low enantioselectivities achieved, functionalized amines were then introduced in these reactions, thereby synthesizing enantioenriched pyrrolopiperazines and other polyfunctionalized heterocyclic molecules, all obtained with attractive yields and high enantioselectivities.Having successfully used methylene β-Ketoamides in these enantioselective MCRs, we realized also that their simple Michael addition to electron-Poor olefins had never been described in organocatalytic conditions. We therefore studied their reaction with nitroolefins in the presence of various chiral organocatalysts, and the expected products were pleasingly obtained with high yields, excellent diastereo- and enantioselectivities
Moreno, Rueda Maryluz. "Hetero-michael addition to sunflower oil derivatives as precusors of polymeric materials." Doctoral thesis, Universitat Rovira i Virgili, 2013. http://hdl.handle.net/10803/128506.
Full textAbstract The principal objective of this thesis is the synthesis of polymeric materials from vegetable oils derivatives. In the first step different flame retardant thermosetting polymers were synthesized through chemical modifications of commercial high oleic sunflower oil followed byaddition and crosslinking via phospha and aza-Michael addition. In the second step lineal polyesters and thermosets were synthesis through thiol-Michael addition to sunflower oil derivatives. The lineal polyesters were modified to wide their biology or biomedical applications. Furthermore the development a novel nanocomposite with cellulose nanocrystal material was carrie out. As general conclusion polymers from vegetables oil derivatives were development successfully
Scansetti, Myriam. "Synthesis of pyroglutamic acid derivatives via double Michael addition reactions of alkynones." Thesis, University of Edinburgh, 2009. http://hdl.handle.net/1842/4222.
Full textFukata, Yukihiro. "Studies on Asymmetric Hetero-Michael Addition Utilizing Various Modes of Organocatalytic Activation." 京都大学 (Kyoto University), 2016. http://hdl.handle.net/2433/215551.
Full textSawicki, Marcin. "Synthèse et criblage de ligands puissants de l'uranyle : application à la décorporation de l'uranium." Paris 11, 2005. http://www.theses.fr/2005PA112075.
Full textThis work was realised as a part of prorgamm "Nuclear Toxicologie" created by CEA and was dedicated to the synthesis of powerfull ligands of uranyl for the applications in decorporation and detection of uranyle. During this work about 200 new potentiales ligands of uranyle was synthesised in the parallele manner using as a key step of the synthesis peptide coupling as well as new parallel synthesis methodology based on the addition of Michael. This library of potencial uranyle ligands, enreached by 100 molecules obtained by collaboration, was submited to high throughput screening test for affinity against uranyle ion using colorimetric agent - sulfochlorophenole S as reference chelate. More then twenty ligands having conditional stability constant against uranyl at pH=7. 4 higher then 10 to 17 were found. All this molecules have methylene biphosphonate unite as chelating function. Beetwen them only one was foun to decorporate uranium in vivo. On the other hand some ligands methylene biphosphoniques were found to forme with uranyle ion the complexes posseding exceptional proprietes of fluorescence what may aloowed for their use for the detection of uranyle
Mehdar, Yassin Taleb. "Synthesis and applications of proline derived guanidine catalysts in asymmetric Michael addition reactions." Thesis, Bangor University, 2017. https://research.bangor.ac.uk/portal/en/theses/synthesis-and-applications-of-proline-derived-guanidine-catalysts-in-asymmetric-michael-addition-reactions(4904fca7-0964-4403-92e5-ed2efe888e85).html.
Full textHoward-Jones, Andrew Glyn. "A synthetic approach to Câ†2 symmetric guanidine bases and the synthesis of model compounds of ptilomycalin A." Thesis, Bangor University, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.340956.
Full textYoung, Douglas M. "Explorations of Cascading Michael Additions." Thesis, University of Oregon, 2011. http://hdl.handle.net/1794/12069.
Full textIntramolecular cascading Michael additions have the ability to transform simple, symmetric substrates into densely functionalized compounds containing new ring structures and chiral centers. The Rauhut-Currier (RC) reaction, also known as the vinylogous Morita-Baylis-Hillman reaction, utilizes this type of reactivity by cyclizing tethered, activated alkenes using phosphine or thiolate catalysis. This dissertation describes the expansion of the scope of the RC reaction, the introduction and importance of co-catalysts to cascading Michael additions, the development of the first amine-catalyzed RC reaction, and the transformation of cyclization products into fused, polycyclic aromatic compounds. Chapter I reviews the development and applications of the Rauhut-Currier reaction. Chapter II describes the regioselective synthesis of di-substituted indenes and introduces phenol as a rate- and selectivity-enhancing co-catalyst. Although tertiary amine nucleophiles were found to be inferior to phosphines as cyclization catalysts, chapter III discusses the ability of unhindered primary and secondary amines to undergo a diastereoselective, cascading aza-Michael-Michael addition to yield a wide variety of amino-indanes in the presence of an acid catalyst. Recognizing the importance of protic environments and small nucleophiles, the development of the first amine-catalyzed intramolecular RC is introduced in chapter IV. Chapter V describes the conversion of methyl ketone-substituted indenes to fluorene derivatives via an intramolecular aldol reaction. Chapter VI describes the serendipitous discovery and synthesis of indenopyrylium salts. Chapter VII details the novel production of indenopyridines from di-substituted indenes. Lastly, chapter VIII provides a summary and suggests future directions for this research. This dissertation includes previously published and unpublished co-authored material.
Committee in charge: Shih-Yuan Liu, Chairperson; Kenneth Doxsee, Advisor; David Tyler, Member; Michael Haley, Member; A. Dana Johnston, Outside Member
Beck, Daniel Antony Speedie, and beckautomatic@gmail com. "Stereoselective intramolecular Michael addition reactions of pyrrole and their application to natural product syntheses." The Australian National University. Research School of Chemistry, 2006. http://thesis.anu.edu.au./public/adt-ANU20070130.130009.
Full textBeck, Daniel Antony Speedie. "Stereoselective intramolecular Michael addition reactions of pyrrole and their application to natural product syntheses /." View thesis entry in Australian Digital Theses Program, 2006. http://thesis.anu.edu.au/public/adt-ANU20070130.130009/index.html.
Full textLewandowska, Urszula. "Spontaneous small molecule migration via reversible Michael reactions." Thesis, University of Edinburgh, 2013. http://hdl.handle.net/1842/10635.
Full textAbdelli, Abderrahmen. "Etude de la réactivité de quelques allylphosphonates β-éthoxycarbonylés." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLV028/document.
Full textDue to the joint presence of several functional groups, β-ethoxycarbonylatedallylphosphonates are considered as excellent precursors for the preparation of neworganophosphorus compounds. In the presentwork, we first described the use of suchphosphonates as Michael acceptors. Indeed, weperformed conjugated additions of thiols,amines and enolate-anion under mild reactionconditions. Allylphosphonates were also usedfor the preparation of a new family of phosphonomethyl α,β-unsaturated γ-lactams.The key step of this sequence is a conjugateaddition of nitroalkanes on allylphosphonates followed by a Nef reaction. Ketoester intermediaites were then convertedinto lactams by reaction with primary amines.Pd-catalyzed arylations on allylphosphonates allowed preparing phosphonated heterocyclesderived from coumarin, quinolinone andbenzoxepinone skeletons. The synthesis of Pheterocyclesof various sizes fromallylphosphonates was explored by theconversion of phosphonate inphosphorochloridate. The reactivity of the latterwith amines, allowed isolation of a new familyof 5-,7-, 8- and 9-membered N,P-heterocycles.The synthesis of 6-membered P-heterocycleshas also been described by performingcyclization under the conditions of a ringclosing metathesis (RCM) starting from bisallylphosphonates and bisallylphosphoramidates
Shoaib, Mohammad [Verfasser]. "Asymmetric Michael Addition of Carbonyl Compounds to Nitro-olefins Catalyzed by Simple Organocatalysts / Mohammad Shoaib." Bremen : IRC-Library, Information Resource Center der Jacobs University Bremen, 2012. http://d-nb.info/1035217015/34.
Full textLombardi, Federico. "Computational study on the asymmetric aminocatalysed Michael addition reaction of cyclohexanone to trans–β–nitrostyrene." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2021. http://amslaurea.unibo.it/23186/.
Full textBurns, Alan Richard. "Intramolecular Michael addition approaches to decalatone natural products : The total synthesis of (+)-dictyosphaeric acid A." Thesis, University of York, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.535069.
Full textBelmessieri, Dorine. "Applications of isothioureas in organocatalysis : kinetic resolution of secondary alcohols and intramolecular Michael addition-lactonisation." Thesis, University of St Andrews, 2013. http://hdl.handle.net/10023/4500.
Full textNadeau, Frédéric. "Le glycérol comme base structurale de coeurs de dendrimères obtenus par addition d'oxa-Michael sur des dérivés acryliques." Thesis, Université de Lorraine, 2017. http://www.theses.fr/2017LORR0357/document.
Full textGlycerol is a bio-based molecule, abundantly available, from the saponification of triglyceride and the transesterification of vegetable oils. The work described in this PhD thesis concerns the use of glycerol as structural base of dendrimer's core, in particular by oxa-Michael addition on acrylic derivatives. The surface functionalization of dendrimers by imidazolium units is explored in order to obtain an ionic liquid dendrimer (DLI) with thermosensitive properties. In the first part, the bibliographic chapter presents the methods of dendrimers synthesis involving acrylic derivatives and their applications and, in a second part, the work introduces the oxa-Michael addition of alcohols to acrylic derivatives. The second chapter deals with the synthesis of the structural base of the dendrimer core from glycerol. The reaction of acylation of glycerol with acryloyl chloride is presented as well as the various constructions of poly(estersulfide) dendrimers from glycerol triacrylate. The nucleophilic addition of glycerol to acrolein, acrylamide, acrylates and acrylonitrile has been studied. With the acrylates, the nucleophilic addition reaction is in competition with the transesterification reaction, with the exception of t-butyl acrylate, resistant in basic medium. With acrylonitrile, the synthesis of 1,2,3-tricyanoethylglycerylether was carried out without solvent in 5 hours at room temperature in the presence of an inexpensive catalyst (4 mol% sodium hydroxide) in a yield of 88% and purity of 99% without purification method. The mono- and di-cyanoethylglycerylether reaction intermediates were characterized and allowed kinetic monitoring of the reaction. The synthesis of poly(amidoamine) dendrimers from 1,2,3-tricyanoethylglycerylether is the subject of the third chapter: synthesis of generations G0 to G2,5 and characterization of dendrimers. The defects in the structure due to intramolecular cyclization have been demonstrated by HRMS for generations Gn and the half-generation dendrimers Gn+5 (n=0, 1, 2) were purified by chromatographic column. Several routes of synthesis for the synthesis of DLI with imidazolium termini are presented
Rosso, Helèna. "Addition conjuguée de réactifs organolithiés : application à la synthèse de produits naturels." Rouen, 2011. http://www.theses.fr/2011ROUES022.
Full textMy Ph. D. Project was mainly focused on the oxa- and carba- Michael additions onto α,β-unsaturated carbonyl compounds. This methodology was investigated for the syntheses of a fragment of a complex natural target compound and natural products. This work has been divided in two parts. In the first part, the partial synthesis of the CD framework of the (-)-azaspiracid I (a dangerous neurotoxic molecule contained in shellfish) was investigated and four strategies were devised in order to synthesize this structure. Instead, the second part explores the reactivity of α,α'-dimethoxy-y-pyrone in order to obtain unsaturated α'-methoxy-y-pyrone plyketides derivatives. For that purpose, we have developed a strategy involving the desymmetrization of α,α'-dimethoxy-y-pyrone by Michael addition. A four-step verticipyrone synthesis is presented. The key steps included the desymmetrization of α,α'-dimethoxy-y-pyrone 1 by conjugated addition with an allylating agent and the cross-metathesis of the allylated pyrone with the proper olefin. Taking advantage of the strategy of the one-pot desymmetrization of pyrone 1 by the addition of an allylating agent, the anion generates during this addition was trapped with an electrophile in order to obtain, in a regio and stereoselective manner, new molecules belonging to the α'-methoxy-y-pyrone family. The bioactivities of these new molecules were also evaluated
Yang, Xuena Verfasser], Dieter [Akademischer Betreuer] [Enders, and Markus [Akademischer Betreuer] Albrecht. "Entwicklung neuer Dominoreaktionen durch Michael-Addition an Nitroalkene als Schlüsselschritt / Xuena Yang ; Dieter Enders, Markus Albrecht." Aachen : Universitätsbibliothek der RWTH Aachen, 2016. http://d-nb.info/1129875830/34.
Full textMcLamore, Dolores Sherita. "Determination of the relative stereochemistry of adducts resulting from the addition lithium dienolates to Michael acceptors." Thesis, Virginia Tech, 1994. http://hdl.handle.net/10919/43137.
Full textMaster of Science
Yang, Xuena [Verfasser], Dieter [Akademischer Betreuer] Enders, and Markus [Akademischer Betreuer] Albrecht. "Entwicklung neuer Dominoreaktionen durch Michael-Addition an Nitroalkene als Schlüsselschritt / Xuena Yang ; Dieter Enders, Markus Albrecht." Aachen : Universitätsbibliothek der RWTH Aachen, 2016. http://d-nb.info/1129875830/34.
Full textZhu, Sunsheng. "Novel Approach to Polyhedral Oligmeric Silsesquioxane-Based Giant Surfactants Basd on Thiol-Michael Addition "Click" Reaction." University of Akron / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=akron1399555570.
Full textNocentini, Benedetta. "Indagine su reazioni di sulfa-Michael di interesse in campo cosmetologico e sul trattamento ricostruttore del capello." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2018. http://amslaurea.unibo.it/15849/.
Full textFuchs, Christian. "Studies towards the total synthesis of the Perophora viridis Trithiocane." Thesis, Loughborough University, 2010. https://dspace.lboro.ac.uk/2134/8577.
Full textAy, Sefer. "Synthese und Anwendung von [2.2]Paracyclophanliganden in der asymmetrischen konjugaten Addition." Berlin Logos-Verl, 2008. http://d-nb.info/992809320/04.
Full textMulliner, Denis. "Quantenchemische Modellierung der Thiol-Addition an Michael-Akzeptoren zur quantitativen Vorhersage ihrer elektrophilen Reaktivität und aquatischen Toxizität." Doctoral thesis, Technische Universitaet Bergakademie Freiberg Universitaetsbibliothek "Georgius Agricola", 2014. http://nbn-resolving.de/urn:nbn:de:bsz:105-qucosa-141274.
Full textMahé, Olivier. "Synthèse organocatalytique de δ2-pyrazolines par addition d’aza-michael et développement d’organocatalyseurs hétérogènes à base de chitosane." Thesis, Rouen, INSA, 2011. http://www.theses.fr/2011ISAM0018.
Full textAn organocatalytic racemic synthesis of 3,5-diaryl pyrazolines was developed, using guanidine as catalyst. Then, an enantioselective synthesis of N-Boc 3,5 diarylpyrazolines under phase transfer catalysis, achieving high enantiomeric excesses up to 94 %. Transprotection reactions of the Boc moiety allowed the introduction of a variety of functional groups on N1 atom of the pyrazolines ring. Finally, we applied this strategy to the synthesis of biologically active pyrazoline. Secondly, we used the chiral biopolymer chitosan in aminocatalysis, as a heterogeneous organocatalyst. We performed chemical modifications either by grafting proline, or by a benzyl moiety leading to secondary polyamines. The obtained materials were tested in different organocatalytic reactions. A 80 % enantiomeric excess has been reached for an aldolisation reaction. Finally, we applied, for the first time, the ionic liquid supported phase strategy on chitossan for aour organocatalysed reactions
Li, Mao. "Iron(III) catalyzed asymmetric Diels-Alder reaction - Iron(II) catalyzed thia-Michael addition and aldehyde allylation reactions." Doctoral thesis, Université Laval, 2019. http://hdl.handle.net/20.500.11794/34969.
Full textIron catalysts are employed in three different organic transformations owing to their advantages: environmental friendliness, being less expensive and abundant on the Earth. The first project deals with asymmetric Diels-Alder reactions of α, β-unsaturated oxazolidin-2-one derivatives catalyzed by Fe¹¹¹ and a chiral bipyridine ligand. In order to obtain the optimized reaction conditions, we screened different solvents, catalyst loading, various reaction times and a variety of iron salts such as Fe(ClO₄)₂·6H₂O, Fe(ClO₄)₂·6H₂O, Fe(OTf)₃, Fe(OTf)₂, FeCl₂, FeCl₃, FeBr₃ and FeI₃. As a result, the reaction between cyclopentadiene and 3-alkenoyl-1,3-oxazolidin-2-one was carried out at –30 °C in CH₃CN in 1.5 h, with Fe(ClO₄)₃·6H₂O (2 mol%) complexed with the chiral bipyridine ligand (2.4 mol%) as catalyst, providing an excellent yield (99%) and an excellent enantiomeric excess (98%). Decreased enantioselectivities were observed for less-reactive dienes. Overall, less than 10 mol% of catalyst loading was employed. The great advantages of this project are the mild reaction temperature, very low catalyst loading, excellent yields and enantioselectivities and the applicability to a wide scope of substrates. Meanwhile, iron catalysts were used in thia-Michael additions by two different approaches. The first one is about thia-Michael additions catalyzed by Fe(OTf)₂ in EtOH at room temperature. This green method allows the thia-Michael additions to be catalyzed by a green iron salt (5 mol% of Fe(OTf)₂), a green and commonly used solvent EtOH at room temperature under ambient atmosphere. The generality of this reaction was demonstrated by applying it to different Michael acceptors, and to aromatic and aliphatic thiols. The second method is about thia-Michael additions catalyzed by Fe(OTf)₂ in 2-Me-THF, which is in agreement with the green chemistry principles by using a green Fe(OTf)₂ and a green solvent 2-Me-THF at room temperature or 50 °C under air atmosphere. The last project is about asymmetric allylation reactions catalyzed by Fe(OTf)₂ using a chiral ligand. With the study of a variety of chiral ligands, we selected 5 mol% of Fe(OTf)₂ and 6 mol% of Pybox ligand which catalyzed the reaction in good yield (70%) and 32% of ee. The utilization of 20 mol% of TMSCl is essential for the effectiveness of the reaction
Li, Zhijian. "Novel solid base catalysts for Michael additions." Doctoral thesis, [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=976576759.
Full textOzturk, Gozde. "Topology and Telechelic Functionality Control in Polyester Design." Diss., Virginia Tech, 2009. http://hdl.handle.net/10919/28030.
Full textPh. D.
Sanchez, Duque Maria del Mar. "Nouvelles applications de l'addition de Michael organo catalysée dans des réactions domino multicomposés énantiosélectives." Thesis, Aix-Marseille 3, 2011. http://www.theses.fr/2011AIX30047.
Full textIn this work, we explored the potential of a Michael addition-initiated multicomponent reaction leading to 2,6-DABCO derivatives. In this context, we first studied the scope of the reaction by changing the partners and the parameters of the reaction. In view of making the process more eco-friendly, the use of ionic liquids was also investigated and found that in some cases, the ionic liquids could replace the toxic organic solvent and the heterogeneous catalyst of the reaction. Finally, the implementation of an enantioselective multicomponent synthesis of 2,6-DABCO led us to develop a new methodology of an organocatalytic enantioselective Michael addition of beta-ketoamides to alpha, beta-unsaturated carbonyls. In this way, adducts containing an all-carbon quaternary stereocenter were obtained in good yields and high to excellent enantiomeric excesses (up to 99%). The study of the reactivity of these adducts allowed the access to different families of optically active poly(hetero)cyclic compounds of high synthetic interest
Fedotova, Alena. "Amines aromatiques stériquement encombrées dans la réaction d'aza-Michael : effets de solvant et haute pression." Thesis, Normandie, 2018. http://www.theses.fr/2018NORMR056/document.
Full textAlong this PhD work, we have reported that the unique combination of hexafluoroisopropanol (HFIP), employed as solvent, and hyperbaric conditions (10-15 kbar) allows unprecedented 1,4-addition of poor nucleophiles such as aromatic amines onto sluggish (cumbersome) Michael acceptors without any promoter nor work-up. Moreover, The hetero-Michael addition of functionally substituted anilines to α,β-unsaturated esters is significantly defined by the difference of acidity between the solvent and the amine. Reaction with more basic anilines proceeds smoothly in methanol. In contrast, very polar protic solvent such as fluorinated alcohols (HFIP and TFE) favor the aza-Michael addition of more weak nucleophiles. Finally, green and catalyst-free method of new amino acid derivatives construction containing adamantane and aziridine fragments was developed. And it is proved that aza-Michael reaction initiates the formation of heterocycle
Flores, Ferrándiz Jesús. "Chiral Aminocarbamates Derived from trans-Cyclohexane-1,2-Diamines as Organocatalysts in Conjugate Addition Reactions." Doctoral thesis, Universidad de Alicante, 2017. http://hdl.handle.net/10045/73589.
Full textEl, Marrouki Dalel. "Contribution à l’étude de la réactivité de quelques accepteurs de Michael cycliques et applications." Electronic Thesis or Diss., Université de Lorraine, 2020. http://www.theses.fr/2020LORR0197.
Full textThis thesis focuses on the synthesis of some nitrogenous heterocycles from the same family of precursors: 1,4-diketones. These 1,4-diketones have been obtained either by a Nef reaction through the conversion of nitro compounds into ketones or by a Wittig reaction using various Wittig ylides and cyclohexanedione. These reaction intermediates were subsequently used for the synthesis of indole derivatives via a 1,2-addition reaction. We were also able to turn the selectivity of the reaction towards the synthesis of indolones from a 1,4-addition reaction. With hydrazine monohydrate, 1,4-diketones have also provided access to cinnolines in excellent yields
Seingeot, Adeline. "Utilisation des liquides ioniques dans des réactions à économies d'atomes : l'addition de Michael et la cycloaddition 1,3-dipolaire." Thesis, Aix-Marseille 3, 2011. http://www.theses.fr/2011AIX30058.
Full textIn the context of sustainable chemistry, an alternative to conventional organic solvents is the use of ionic liquids. These works reported here aims to describe the use of ionic liquids (IL) in two atoms economy reactions, namely the Michael addition reaction and 1,3-dipolar cycloaddition catalyzed (or not) by a copper salt (CuAAC). In the first part of the work reports the use of Super-Acid Ionic Liquids (SAIL), which initiate an electrophilic activation. After optimization of SAIL on a reaction model, application to other electrophiles and nucleophiles is discussed. The purity of SAIL affects the chemioselectivity: if the SAIL is partially hydrolyzed, a Robinson annulation predominates. The asymmetric version of the process is investigated, showing that it is possible to carry out an enantioselective reaction with amino acid derived SAIL. The second part of the study deals with setting up an original synthesis of (triazolylmethyl)vinylphosphonate from acetoxymethylvinylphosphonate using a one-pot procedure involving a 1,3-dipolar cycloaddition in different LI. We further showed that the ionic liquid can also act as an activator for this reaction
Ji, Mingzhe. "Explorations with optically active, cage-annulated crown ethers." Thesis, University of North Texas, 2003. https://digital.library.unt.edu/ark:/67531/metadc4207/.
Full textRichard, Mylène. "Les exo-glycals activés pour la synthèse de dérivés saccharidiques complexes : application à la préparation de glycoamino acides et de peptidomimétiques." Thesis, Université de Lorraine, 2015. http://www.theses.fr/2015LORR0133/document.
Full textThis work is focused on the development of new synthetic pathways for exo-glycals functionalization and synthesis of bioactive compounds. The first part of this manuscript describes the efficient preparation of new tertiary S-glycosides and γ-glycoamino acids via Michael addition of thiols derivatives and carbanions on anomeric carbon of exo-glycals. The obtained γ-glycoamino acids were then incorporated in α/γ mixed peptides and their structural properties were studied by NMR, IR, CD and molecular modelling studies. Furthermore, cyclic multivalent platforms were built by intramolecular cyclization of these entities. The second part of the manuscript concerns the elaboration of peptidomimetics targeting neuropilin-1 receptor, implicated in tumor angiogenesis. Based on molecular modeling studies, some compounds showed interesting binding affinity for NRP-1 receptor and one of them displayed promising properties toward inhibition of tubule formation
Raimondi, Wilfried. "Nouvelles transformations organocatalysées énantiosélectives à partir de composés dicarbonyles et de nitroalcènes." Thesis, Aix-Marseille, 2012. http://www.theses.fr/2012AIXM4350/document.
Full textThis work focused on the development of novel transformations combining MBFT's and organocatalysis, the latest powerful tools of organic synthesis, and involving the reactivity of nitroalkenes. We first developed a highly stereoselective consecutive Michael – [3+2] Heterocyclisation – Fragmentation reaction where two C–C bonds, one C–O bond and a cycle are formed to make optically active cyclopentanoximes bearing up to three stereocenters. These products can be converted into hydroxylamines or indoles. We then exploited the nucleophilic potential of 1,2-dicarbonyl compounds in the design of the first organocatalyzed diastereo- and enantioselective Michael additions of 1,2-ketoamides and 1,2-ketoesters onto nitroalkenes. The corresponding adducts are valuable synthetic platforms towards the synthesis of five- and six-membered carbo- and heterocycles with wide functional variety. This work led to the development of a domino transformation involving 1,2-dicarbonyl compounds and halogenated nitroolefines to efficiently access 2-carbonyl- and 2-phosphorylfuranes whose reported synthetic pathways remain rare. The first encouraging trials carried out to make atropisomers enable a potential asymmetric version of this methodology
Léger, Frédéric. "Additions d'énamines β-lithiées sur des esters α, β-éthyléniques. Nouvelles propriétés des énamines β-halogénées." Rouen, 1996. http://www.theses.fr/1996ROUES051.
Full textHoffmann, Guillaume. "Mise au point de nouveaux descripteurs théoriques pour la réactivité chimique Can molecular and atomic descriptors predict the electrophilicity of Michael acceptors? On the influence of dynamical effects on reactivity descriptors Predicting experimental electrophilicities from quantum and topological descriptors : a machine learning approach Electrophilicity indices and halogen bonds : some new alternatives to the molecular electrostatic potential." Thesis, Normandie, 2020. http://www.theses.fr/2020NORMR042.
Full textThe study of global, local and non-local reactivity descriptors of a reactive system is of paramount importance in order to understand the reactivity of all chemical processes during a reaction. The goal of this thesis was then to develop new reactivity descriptors, as well as prediction models based on them, in order to study chemical reactivity. The main theoretical methods used were the Conceptual Density Functional Theory (CDFT) and Quantum Theory of “Atoms in Molecules” (QTAIM), which are both based on electron density. Our field of study is mainly within the framework of the Mayr experimental scale, which allows, through kinetic measurements a classification of molecules in order of reactivity. In the first part, great advances were made during this thesis with respect to the theoretical prediction of experimental electrophilicity of Michael acceptors. Then in a second step, we looked at the application of reactivity descriptors on the chemical bond, and in particular the halogen bond. Finally, a part of synthesis carried out during the course of this thesis is presented, by proposing a new way of synthesis of vinylogous iminium cations