Dissertations / Theses on the topic 'Copper-catalyzed 3+2 cycloaddition'

Le premier objectif de ce travail a consisté à développer la réaction CuSAC (découverte au laboratoire) pour la synthèse régiosélective de pyrazoles poly-substitués, dans un contexte de méthodologie de synthèse. Il existe de nombreux composés biologiquement actifs contenant le motif pyrazole et peu de méthodes régiosélectives décrites pour les synthétiser. Développer une nouvelle réaction pour obtenir des pyrazoles poly-substitués de façon contrôlée était donc très intéressant pour des applications synthétiques.Le deuxième objectif a été d’appliquer cette réaction à la bioconjugaison et notamment au développement de sondes profluorescentes Des coumarines-sydnones subissant un effet d’extinction de fluorescence par le phénomène PeT ont été développées. Suite au couplage avec un alcyne, le pyrazole formé n’éteint plus lafluorescence de la coumarine. Ce type de sondes est très intéressant pour le marquage de biomolécules, car il n’y a aucun parasitage de fluorescence et donc ne nécessite aucun lavage.Le troisième objectif de la thèse a été d’explorer la réactivité des composés mésoioniques pour un alcyne, sous une catalyse au cuivre, dans le but de découvrir de nouvelles réactions click. Un criblage de 24 composés dans 9 conditions de catalyses différentes, faisant plus de 200 réactions réalisées, a été effectué. Deux réactions ont été révélées, dont une très prometteuse. Celle-ci permet dans la même opération de lier deux partenaires tout en libérant un fragment d’un des deux partenaires. Cette réaction a été étudiée dans le but de développer un outil de théranostique où être utilisée pour la mise au point de nouveaux espaceurs clivables
The first aim of this work was the development of a new regioselective synthetic access to poly-substituted pyrazoles via the CuSAC reaction, previously discovered in the laboratory. The development of new reactions leading to poly-substituted pyrazoles with a full control of regioselectivity is highly interesting for synthetic applications.The second aim of this work was the application of this reaction for the labeling of complex biomolecules. To broaden the scope of the CuSAC, fluorogenic coumarin-sydnones which undergo fluorescence extinction via PeT have been designed and synthetized. Following the coupling reaction, the newly formed pyrazole core allows huge enhancement of the fluorescence signal.This kind of probes is highly interesting in the specific labelling of biomolecules avoiding washing steps.The last project of this thesis have been focused on the discovery of new [3+2] cycloaddition reaction implying a mesoionic compound and a terminal alkyne under copper catalysis. 24 mesoionic dipoles were screened for their ability to react with a terminal alkyne in 9 different catalytic conditions, yielding to more than 200 reactions screened. Two hits were identified, one of them holding great promise. This hit allows an efficient “click and release” reaction which should find tremendous applications, especially in the fields of theranostic and cleavable linker development

Cette thèse est constituée de trois parties : 1) Le contexte bibliographique, 2) le développement de réactions domino cupro-catalysées et 3) une approche vers la synthèse totale des raputindoles.La première partie introduit d’abord le concept de réactions domino ainsi que leurs applications, puis les réactions catalysées par du cuivre permettant de former des liaisons C-N sont passées en revue en incluant les couplages de Ullmann, Goldberg et de Chan-Lam, les séquences d’activation oxydante de liaisons C-H/formation de liaison C-N, l’insertion de nitrènes et l’hydroamination de liaisons C-C multiples. En se basant sur ces réactions élémentaires permettant de former une liaison C-N unique, les développements récents de réactions domino sont ensuite détaillés.La deuxième partie peut être subdivisée en 3 sections : 1) la synthèse de benzimidazoles, 2) la synthèse d’imidazoles and 3) la synthèse de guanidines. Un rappel des méthodes existantes pour la synthèse de ces motifs est proposé dans chaque section. Notre travail, basé sur la formation de liaisons C-N multiples selon une séquence cupro-catalysée domino, est ensuite détaillé. Celui-ci nous a permis d’aboutir au développement de voies d’accès aux benzimidazoles, en utilisant une réaction séquentielle catalysée par du cuivre en présence d’oxygène à partir d’acides boroniques et d’amidines, à la synthèse d’imidazoles par une réaction de di-amination d’alcynes vrai par des amidines et à l’obtention de guanidines et de 2-aminobenzimidines par une réaction à 3 composant. Ces réactions domino montrent une bonne efficacité et permettent d’assembler des hétérocycles à partir de précurseurs aisément accessibles.La dernière partie est consacrée à la synthèse des raputindoles. La structure, les activités et les réactions clé pour la construction de ces alcaloïdes sont discuté d’abord, nous amenant à proposer une rétrosynthèse pour accéder à ces molécules. Les réactions qui ont retenues notre attention pour construire ces molécules sont une annelation [3+2] irido-catalysée d’acides o-formylarylboronique et de 1,3-diènes, la synthèse de Leimgruber-Batcho pour obtenir des indoles et une séquence d’alkylboration-protodéboration. A partir de cela 3 stratégies ont été évaluées, montrant que l’accès à ce type de composé naturel est envisageable en combinant ces étapes
This thesis consists in three parts: bibliographic background, copper-catalyzed reactions for synthesis of N-containing compounds, approach to the synthesis of raputindoles.The first part introduces the domino reactions and their applications, then, copper-mediated reactions for construction of C-N bond formation are reviewed including Ullmann, Goldberg and Chan-Lam coupling, oxidative C-H activation/C-N formation, insertion of nitrenes and carbenoids, and hydroamination of multi-C-C bonds. This can be used as guides to design domino reaction. Following these copper-mediated single C-N bond formation reactions, recent developments of copper-catalyzed domino reactions for synthesis of heterocycles are described.The second part can be divided into three sections: 1) synthesis of benzimidazoles, 2) synthesis of imidazoles and 3) synthesis of guanidines. Each section summarizes the existing methods used for their synthesis. Following it, our synthetic work involving copper-catalyzed C-N bond formation domino reactions is discussed in detail. Our objectives include the synthesis of benzimidazoles through copper-catalyzed sequential reaction of benzamidines and boronic acids, synthesis of imidazoles via copper-catalyzed domino reaction of benzamidines and acetylenes, and synthesis of guanidines and 2-aminobenzimidazoles by Cu-catalyzed three-component reaction of cyanamides, boronic acids and amines. These copper-catalyzed domino reactions show high efficiencies from readily available and simple starting materials.The last part is about the total synthesis of raputindoles. The structure and bioactivities of raputindoles and key reactions for the total synthesis of raputindoles are introduced first, the synthetic strategies are then proposed on basis of relative synthetic methods. The key reactions we use for the synthesis of raputindoles are iridium catalyzed [3+2] annulation of o-formylarylboronic acids and 1,3-dienes, Leimgruber-Batcho indole synthesis, transition-metal catalyzed SN2 substitution and alkylborylation-protondeborylation. According to the three strategies we proposed, lots of relative reactions were investigated. The results show that it is possible to synthesize the raputindole molecules based on the iridium catalyzed [3+2] annulation of 2-formylarylboronic acids and 1,3-dienes

碩士
國立清華大學
化學系
103
In first chapter describes the copper-catalyzed [2+2]-cycloaddition of hydroxylamines with terminal alkynes in oxygen atmosphere to form corresponding β-lactams derivatives. β-lactam functionality commonly found in many natural products as well as biologically active molecules. The utility of this [2+2]-cycloaddition is manifested by wide scope of hydroxylamines and terminal alkynes. The second chapter describes one-pot copper-catalyzed [3+2]-cycloaddition of hydroxylamine with allene ether in oxygen atmosphere to form isoxazolidine derivatives. The use hydroxylamines provides a more convenient method to access isoxazolidine derivatives through insitu generated nitrone.

The iridoids are a large family of monoterpenoid natural products that possess a wide range of biological activities. A great deal of research has already been done in the field of iridoid total synthesis, but limitations still remain. Specifically, few syntheses of iridoid β-glycosides have been reported. This work describes the 14 step asymmetric total synthesis of the iridoid β-glycoside (+)-geniposide utilizing a phosphine-catalyzed [3+2] cycloaddition as the key step. Other noteworthy steps in the synthesis include a palladium-catalyzed kinetic resolution and a previously unutilized method for iridoid glycosidation. In addition to describing the synthesis of (+)-geniposide, this dissertation will also review 1) phosphine-catalyzed cycloaddition reactions and 2) previous enantioselective total syntheses of iridoid glycosides.
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Over the last decade, the domain of click chemistry has grown exponentially and has significantly impacted the fields of organic synthesis, medicinal chemistry, molecular biology, and materials science. The ideal model of a click reaction has become the copper-catalyzed azide-alkyne cycloaddition (CuAAC). Inherent limitations of CuAAC, including high temperatures, long reaction times, and difficult purifications, have been minimized by the development of nitrogen-based ligands. Herein, we present a novel application of 1,2,4-triazines by investigating their use as accelerants for CuAAC. A diverse library of 1,2,4-triazines were synthesized in order to examine the molecular determinants of their catalytic activity. These ligands were found to be potent accelerants, at catalytic concentrations, in the presence of both copper(I) and copper(II) salts. Remarkably, these catalyzed reactions proceeded at room temperature, generating high isolated yields, in both polar and nonpolar solvents. 5,6-Diphenyl-3-(pyridin-2-yl)1,2,4-triazine was the most active ligand studied, producing an 89% yield in a model click reaction within one hour. Additional experiments with an array of azides and alkynes yielded similar results, defining a broad substrate scope for 1,2,4-triazines as catalysts for click chemistry. Heterogeneous 1,2,4-triazines were designed using different solid supports and different sites of attachment with respect to the 1,2,4-triazine ligand. The primary advantages offered by these immobilized catalysts are the prevention of metal contamination in 1,2,3-triazole products and the recyclability of the catalyst. Results indicated that 1,2,4-triazine-functionalized silica was a more effective accelerant of CuAAC, whereas polystyrene-supported 1,2,4-triazines displayed modest activity. In coordination with copper(II), 1,2,4-triazines appended onto silica generated isolated yields greater than 90% after four consecutive reaction cycles with minimal copper leaching. Further research will utilize both homogeneous and heterogeneous 1,2,4-triazine-accelerated CuAAC in the derivatization of solid supports for energy-related chemical processes and in the synthesis of novel enzyme inhibitors.

博士
國立清華大學
化學系
99
In the thesis, a CoI2/(R)-BINAP, Zn, ZnI2 and H2O system efficiently catalyzed the intermolecular asymmetric reductive coupling of alkynes (1a-1g) with cyclic enones (2a-2d) at room temperature for 24 hour to afford highly enantioselective β-substituted cyclic enones. The reaction proceeds with highly regio- and stereoselectivity. In addition, by identify the absolute configuration of products 2.3a and 2.3f, a possible mechanism that involves the formation of cobaltacyclopentene intermediate from alkyne and cyclic enone is proposed. In addition, two different catalyzing system: CoBr2/dppe, Mn, ZnCl2, CH3CN and CoI2/BINAP, Zn, ZnI2, 1,4-dioxane, efficiently catalyzed the intermolecular reductive [3+2] cycloaddition of alkynes (1a-1l) with cyclic enones (2a-2e) at 40oC for 24 hour to afford highly stereoselective bicyclo[2.2.1]hept-2-en-1-ol and bicyclo[3.2.1]oct-6-en-1-ol derivatives respectively. This reaction also expanded a new reaction type of alkynes and enones in transition metal catalyzed reaction. We utilized the isotope experiment to further understand the mechanism. . Finally, we developed a new system: CoI2/(R,R′,S,S′)-Duanphos, Zn, ZnI2, 1,4-dioxane, efficiently catalyzed the intermolecular asymmetric reductive [3+2] cycloaddition of alkynes (1a-1i) with cyclic enones (2a-2e) at room temperature for 24 hour to afford highly enantio- and stereoselective bicyclo[2.2.1]hept-2-en-1-ol and bicyclo[3.2.1]oct-6- en-1-ol derivatives. In addition, by identify the absolute configuration of products 3.3a, a possible mechanism that involves the formation of cobaltacyclopentene intermediate from alkyne and cyclic enone is proposed. We discussed the result depend on alkyne and enones by asymmetric reductive coupling and asymmetric reductive [3+2] cycloaddition experiment, and further investigate the interdependent between these two reactions

This thesis is an investigation of ruthenium-catalyzed [2+2] cycloaddition reactions of a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with unsymmetrical alkynes. Yields of up to 90% were obtained though regioselectivity was modest. Select cycloadducts could be separated and used to access a highly functionalized [3.2.0] bicyclic structure through reductive cleavage of the N-O bond. These ring-opened products displayed a chemical exchange phenomenon in 1D carbon NMR and required characterization by 2D NMR techniques. In addition, a haloalkynylation reaction was found to occur when 1-iodo-2-phenylethyne and the 3-aza-2-oxabicyclo[2.2.1]hept-5-ene were submitted to the cycloaddition conditions. An effort was made to optimize the reaction between 1-iodo-2-phenylethyne and norbornadiene in favour of the addition product.
Government of Ontario, NSERC

碩士
高雄醫學大學
醫藥暨應用化學研究所碩士班
94
英文摘要 Recently, we developed synthetic methods to a series of aromatic compounds such as isoquinolone, phenanthridinones, and biphenyls via anionic cycloaromatization of enediynes. As part of ongoing research to synthesis benzo[c]coumarins, we found that treatment of methyl 2-(3(Z)-undecen-1,5-diynyl)benzoate with 1 eq PdCl2 in refluxing CH3CN afforded benzo[c]coumarin (47a) in 65% yield. This reaction could be carried out by using 5 mol % PdCl2 and two equivalents of CuCl2 in refluxing CH3CN. A series of benzo[c]coumarins were prepared according to this method and the yields are 11-65%. The combination PdBr2 (5 mol %) and CuBr2 (2 eq) are also found to effect the cyclization reactions.

碩士
中山醫學大學
應用化學系碩士班
99
Optical active β-cyclodextrin (β-CD) often serves as the chiral selector for the separation of enantiomers. However, because of its higher C7 symmetry and non-ionic peripherals, β-CD only shows moderate chiral discrimination efficiency toward limited racemic pools. In the present research, mono- and bis-poly (amido amine) (PAMAM) dendrons-substituted β-CD derivatives were successfully synthesized to reduce the intrinsic symmetry of unmodified β-CD and to yield multiple positive charges on the primary face. G1 and G2 NH2-terminated PAMAM dendrons were prepared through divergent pathway using propargylamine as the focal point, and then copper(I)-catalyzed Huisgen [2 + 3] dipolar cycloaddition reaction (click reaction) successfully conjugated the azide-functionalized β-CD and thus-prepared PAMAM dendrons. Mono and bis-adduct were obtained by the conjugation of mono-azido-functionalized β-CD with the G2 PAMAM dendron and by the coupling of regioselective 6A,6D-bis(azido)-substituted β-CD with two G1 PAMAM dendrons via click reaction, respectively. After dialysis and lyophilization to give final highly water-soluble β-CD/PAMAM complexes, the protonation level of internal tertiary amines and peripheral primary amines was adjusted by pH titration. The 1H NMR analysis clearly indicated that the primary amines were completely protonated but the tertiary amine remains in neutral state at neutral pH, which allows us to control the charge density of these β-CD derivatives by using suitable pH buffer. We also anticipate the mono and bis-PAMAM-substituted β-CD derivatives, bearing lower C1 and C2 symmetry and multiple positive charges, could be the considerable chiral selectors for the separation of anionic enatiomeric pairs.

博士
國立清華大學
化學系
103
In the first part of this thesis, we reported the synthesis of glycosyl azides from peracetylated sugars (or glycosyl trichloroacetimidates) using VO(OTf)2 as the catalyst which can improve 1,2-trans selectivity to understand the role of this oxometallic species, we monitor the reaction progress by 1H NMR spectroscopic analysis of the reaction mixtures to confirm the different catalytic exerted by VO(OTf)2. An intermediate resulting from glycosyl rearrangement to α-form starting materialwas identified in the catalytic reaction mediated by TMSOTf. This novel vanadyl triflate also provided access to catalyze azidation of various, disaccharides and trisaccharides in high 1,2-trans stereoselectivity and good yields (92-99 %) under mild conditions in CH2Cl2. Not only does VO(OTf)2 enhance β-stereoselective glycosyl azidation but also avoids the rearrangement of C2 acetate group and the formation of orthoester byproducts. The second part is dealt with azide-alkyne cycloaddition (CuAAC) in mild and green conditions by a combination of VOSO4 and Cu(0) for in-situ generation of Cu(I) in aqueous media. Vanadium compounds can exist in oxidation states ranging from -3 to +5 and their interconversion between different oxidation states is achieved by one-electron redox process. Its intrinsic redox nature permits the catalysis of a wide range of organic reactions by judicious combination with suitable metal reductants. Through an extensive survey of various conditions, we have established an effective recipe to generate Cu(I) speceies for the CuAAC reaction in both homogeneous (CH3CN) and heterogeneous (Methanol, t-BuOH/H2O, H2O) solvent systems. In this new click reaction, mild acidic condition plays an important role to stabilize the incipient Cu(I) species and a pronounced ligand effect on the vanadyl species is observed. This new catalytic methodology is attractive because it can be applied to aqueous solution which is important in biological systems at ambient temperature and physiologic pH conditions. In the third part, we have disclosed an elegant and pragmatic catalytic system by using VO(OTf)2 catalyst for 1.2-trans β-selective and 1,2-cis α-selective glycosylationof thioglycosides. The catalytic strategy described herein can achieve stereospecific glycosylation in excellent yields. When low-concentration (10 mM) mixed solvent systems (CH2Cl2-CH3CN-EtCN) with N-Iodosuccimide (NIS, 1.25 equiv) as the activator was employed, preferential 1.2-trans glycosides(-selectivity) was attained. When VO(OTf)2-xCH3CN was used as a solution in DMF for catalytic glycosylation, highly 1,2-cis (α-selectivity) glycosylation was achieved. Finally, a reduced loading of VO(OTf)2-xCH3CN (3M in DMF) to 0.05 equiv still led to efficient catalysis and 1,2-cis -selective glycosylation can still be maintained. In the second chapter of this thesis, a series of oxometallic species and metal acetylacetonates (acac) was examined as catalysts for oxidative beta-carbonylation of styrenes with benzaldehyde by using t-butylhydroperoxide as co-oxidant and trapping agent in warm acetonitrile. Among them, VO(acac)2 and vanadyl(IV) chloride were found to be the only two catalyst classes to achieve the cross-coupling processes by judicious turning the ligand electronic attributes, leading to β-hydroxylation and β-peroxidation of styrenes, respectively, in a complementary manner. Mechanistic studies indicated that vanadyl associated, acyl radicals generated by t-butoxy radical-assisted, homolytic cleavage of aldehyde C-H bond were involved in the tandem processes with exclusive syn diastereoselectivity in the case of -methylstyrene.

Le traitement du cancer est l’un des plus grands défis en chimie médicinale moderne. La majorité des traitements utilisés repose sur la chimiothérapie, impliquant l’emploi de molécules bioactives cytotoxiques. Bien qu’efficaces, ces molécules présentent, pour la plupart, des désavantages notoires tels que le manque de spécificité cellulaire et une solubilité limitée en phase aqueuse. Une façon de remédier aux problèmes exposés est de solubiliser ces molécules au sein de matrices polymères. Il existe différents types de matrices qui sont : les liposomes, les micelles, les nanosphères, les nanocapsules, les dendrimères (et les polymères en étoile), et les polymères conjugués et linéaires. Dans cette thèse, nous faisons l’étude de deux matrices polymères potentielles composées de matériaux biocompatibles : le polylactide et la poly(2-isopropyl-2-oxazoline). La première partie de la thèse, est consacrée à l’étude des polyester-co-éthers portant des groupements pendants fonctionnalisables. Nous avons développé ces copolymères par polymérisation aléatoire en masse de lactones (le lactide ou la caprolactone) et différents taux d’éthers de propargyle et de glycidyle (GPE), à 120°C, en utilisant l’octanoate d’étain comme catalyseur. L’efficacité de la copolymérisation a été mise en évidence par des analyses FTIR, RMN 1H et COSY. Toutefois, L’analyse GPC a montré une diminution de la masse molaire des polymères et un élargissement de la dispersité en rapport avec l’augmentation du taux de glycidyle initial. De plus, les analyses RMN 1H ont montré que le taux de propargyl (provenant de l’éther de glycidyle) au sein du copolymère ne dépassait pas 50%. La faisabilité des modifications post-polymérisation a été évaluée en couplant le (9-azidomethyl) anthracène au chaîne de poly(ester-co-éther)s via la chimie clic CuAAC. Cette méthode s’est révélée inoffensive pour la chaîne de polyesters. Des études de cytotoxicité ont prouvé l’innocuité des poly(ester-co-éther)s. Des nanoparticules sphériques ont été préparées à partir de ces polymères et peuvent être utilisées comme nanosphères pour le transport de molécules bioactives hydrophobes. La copolymérisation des lactones avec des éthers de glycidyles s’avère être une stratégie intéressante de fonctionnalisation des chaînes des polyesters permettant la synthèse d’une large gamme de copolymères pour des applications biomédicales. Afin d’améliorer la synthèse des poly(ester-co-ether)s, nous avons proposé une approche mécanistique tenant compte des réactions de transfert de chaînes. Dans la deuxième partie de la thèse, nous avons étudié un polymère en étoile composé d’un polymère thermosensible : la poly(2-isopropyl-2-oxazoline) PIPOZ. Nous avons premièrement exploré deux approches synthétiques afin d’obtenir une série d’étoiles de PIPOZ (S-PIPOZ) de structure bien définié à savoir l’approche « coupling-onto » et l’approche « core-first ». Une première série de S-PIPOZ a été réalisée directement à partir d’un coeur pentaérythrityl tétratosylés par polymérisation cationique par ouverture de cycle (CROP) de 2-isopropyl-2-oxazoline pour l’approche « core-first ». Pour l’approche « coupling-onto », une deuxième série de S-PIPOZ a été réalisée par couplage via la CuAAC entre des PIPOZ-N3 linéaire (L-PIPOZ N3) et un cœur à 4 bras portant des alcynes terminaux. Tous les S-PIPOZs obtenus ont été analysés par RMN 1H, IR, MALLS-LS, des analyses UV et par microcalorimétrie différentielle à balayage (HS-DSC). Les polymères obtenus par l’approche « core-first » ont montré une microstructure mal-définie comparé à ceux obtenus par l’approche « coupling-onto ». Suite à ces résultats, nous avons défini l’approche « coupling-onto » comme voie d’obtention des S-PIPOZ. Une explication sur la structure mal-défini des polymères obtenus par l’approche « core-first » sera développée dans cette section. Nous exposerons aussi une méthode de purification permettant l’élimination rapide et efficace des L-PIPOZ N3 qui contaminent les échantillons de S-PIPOZ faits par l’approche « coupling-onto ». Cette méthode peut être applicable à d’autres polymères thermosensibles dans une certaine gamme de température. Dans la troisième partie, nous avons étudié l’effet de l’architecture et de la composition des bras-polymères sur la température de transition de phase et les propriétés des S-PIPOZs. Afin d’étoffer notre étude nous avons synthétisé un polymère en étoile à bloc composé de PIPOZ et de poly(éthylène glycol) PEG. Cette étude a été réalisée en examinant des solutions chauffées de polymères (S-PIPOZ, S-PIPOZ-b-PEG et tous les précurseurs linéaires) par des analyses de spectrométrie d’absorption UV, HS-DSC, diffusion de la lumière LS. Nous avons évalué la présence ou l’absence de cristaux au sein d’échantillons de S-PIPOZs provenant de solutions chauffées. Cette évaluation a été réalisée par diffusion des rayons-X aux grands angles (WAXS) et par microscopie électronique à transmission (TEM) et à balayage (SEM). La présence de cristaux est néfaste pour la conception de nanomatériaux destinés à des applications biomédicales. Nous exposons aussi dans cette section une méthode basée sur l’amination réductrice permettant de fonctionnaliser les S-PIPOZ avec différents types de macromolécules. Cette thèse expose les avantages et les inconvénients (synthèses, fonctionnalisation, structures…) des PLA-co-GPE et des S-PIPOZs et constitue dans son ensemble à une première ébauche vers une conception améliorée de futurs nanomatériaux.
Treatment of cancer is one of the biggest challenges in modern medicinal chemistry. The vast majority of treatments are based on chemotherapy, involving the use of cytotoxic bioactive molecules. Although effective, most of these bioactive molecules have notorious drawbacks, such as the lack of cellular specificity and limited solubility in aqueous media. A way to address these problems is to dissolve these bioactive compounds into polymer matrices. There are different types of matrices, including liposomes, micelles, nanospheres, nanocapsules, dendrimers (and star-polymers), and conjugate and linear polymers. In this thesis, we explored two different prospective polymers that can be used as matrices. Both are composed of biocompatible materials: polylactide and poly(2-isopropyl-2-oxazoline). The first part of the thesis is dedicated to the investigation of polyester-co-ether with functionalizable pendant groups. First, we developed the polyester-co-ether by copolymerization of lactones (lactide or caprolactone) with different ratios of glycidyl propargyl ether (GPE) in the bulk at 120°C in the presence of Sn(Oct)2. The efficiency of the copolymerization was evidenced by FTIR, 1H and COSY NMR analyses. However, GPC analyses displayed a decrease of molecular weights and a broadening of the molecular weight dispersity with increasing of the epoxide molar ratio in the feed. 1H NMR analyses showed that the propargyl content from the epoxide does not exceed 50%. The feasibility of post-polymerization functionalization was evaluated by coupling anthracene to the poly(ester-co-ether)s through copper-catalyzed alkyne-azide cycloaddition (CuAAC). The polyester chain was found to support this reaction. Toxicity studies showed that the poly(ester-co-ether) was non-toxic. Spherical nanoparticles were prepared from these polymers. They can be suitable nanospheres for drug delivery. The copolymerization of lactone with glycidyl ether is an interesting approach to functionalize the PLA (or poly(ester)) main chain. It is also a powerful and straightforward strategy to synthesize a large array of functionalized polymers for biomedical applications. In order to improve the synthesis of the polyester-co-ether, we investigated the copolymerization mechanism of the chain transfer reactions leading to the chain reductions and we suggested a mechanistic explanation. In the second part of this thesis, we focused on developing star-polymers from the thermosensitive (2-isopropyl-2-oxazoline) polymer. In order to prepare a well-defined set of star-poly(2-isopropyl-2oxazoline) S-PIPOZs, we explored two different synthetic approaches: the “coupling-onto” and the “core-first” approach. Two sets of S-PIPOZs were prepared by these approaches. For the “core-first” approach, a set of S-PIPOZ was prepared by direct cationic ring opening polymerization (CROP) from a tetra tosylate-functionnalized pentaerythrityl core. For the “coupling-onto approach”, the S-PIPOZs were prepared by ligation between L-PIPOZ-N3 and a 4-arm core with an alkyne group via CuAAC. The prepared polymers were analysed by 1H NMR, IR, Multi Angles Laser Light Scattering - Gel Permeation Chromatography (MALLS-GPC), UV absorption spectroscopy and High Sensitive Differential Scanning Microcalorimetry (HS-DSC). Polymers obtained by the “core-first” approach shows ill-defined microstructure compared to those obtained by the “coupling-onto” approach. In light of these encouraging results, the “coupling-onto” method was pursued for preparing S-PIPOZ. An explanation on the ill-defined structure will be provided within this thesis. Moreover, we developed a purification method for the fast and efficient removal of free PIPOZs, which otherwise contaminate the star-PIPOZ samples that are prepared by the coupling-onto approach. This method is applicable to other thermosensitive polymers within a certain range of temperature. In the third part, we focused on the effect of the architecture and composition of the S-PIPOZs on the phase transition temperature of the polymer. For this, we synthesized a hetero-star block copolymer composed of PIPOZ and poly(ethylene glycol) PEG. This study was carried out by examining the aqueous polymer solution (the linear precursors, S-PIPOZs, S-PIPOZ-b-PEG) upon heating via UV spectroscopy, HS-DSC and light scattering. We also assessed the temperature-induced crystallinity of the Star-PIPOZs by Transmission (TEM) and Scanning (SEM) Electron Microscopy, WAXS. This is important for biomedical nanodevices. We also provided a straightforward method, based on aminative reduction, to functionalize the S-PIPOZ with different macromolecules. This thesis discusses the advantages and the drawbacks related to the synthesis, functionalization, structures of PLA-co-GPE and the star-PIPOZs. Overall, this represents a pioneering study for improving the design of prospective nanodevices.