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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Studies Toward the Completion of the C29-C51 Segment of Spongistatin 1

Stewart, Catherine A. 10 September 2008 (has links)
No description available.
12

Engaging Esters as Cross-Coupling Electrophiles

Ben Halima, Taoufik 09 August 2019 (has links)
Cross-coupling reactions, where a transition metal catalyst facilitates the formation of a new carbon-carbon or carbon-heteroatom bond between two coupling partners, has become one of the most widely used, reliable, and robust family of transformations for the construction of molecules. The Nobel Prize was awarded to pioneers in this field who primarily used aryl iodides, bromides, and triflates as electrophilic coupling partners. The expansion of the reaction scope to non-traditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. The major goal of this thesis research is to improve and expand upon this field by using esters as electrophiles via the activation of the strong C(acyl)−O bond. Esters are particularly robust in comparison to other carboxylic acid derivatives used in cross-coupling reactions. Success on the activation of such inert functional group using catalysis has both fundamental and practical value. By discovering new reaction modes of this abundant functional group, synthetic routes to access novel or industrially important molecules can be improved. Chapter 1 of this thesis describes a literature overview of what has been accomplished in the field of cross coupling reactions using carboxylic acid derivatives as electrophilic coupling partners. Chapter 2 discloses the first palladium Suzuki-Miyaura couplings of phenyl esters to produce ketones. The method is efficient and robust, giving good yields of useful products. The reaction is proposed to proceed via an oxidative addition to the strong C(acyl)−O bond of the ester. In contrast to previous efforts in this field that use traditional catalysts such as Pd(PPh3)4, the developed reaction requires use of an electron-rich, bulky N-heterocyclic carbene ligand, which facilitates the strong bond activation. Furthermore, a palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via a similar activation of the C−O bond by oxidative addition with a Pd−NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases to react. Chapter 3 discloses a nickel-catalyzed amide bond formation using unactivated and abundant esters. In this transformation, an accessible nickel catalyst can facilitate the activation of diverse aliphatic and aromatic esters to enable direct amide bond formation with amines as nucleophiles. No stoichiometric base, acid, or other activating agent is needed, providing exceptional functional group tolerance and producing only methanol as a by-product. This reaction is of both fundamental and practical importance because it is the first to demonstrate that simple conditions can enable Ni to cleave the C–O bond of an ester to make an oxidative addition product, which can be subsequently coupled with amines. This discovery contrasts industrially-common and wasteful methods that still require stoichiometric activating agents or multistep synthesis. Chapter 4 describes the evaluation of different types of cross-coupling reactions using methyl esters as electrophilic coupling partner. A high-throughput screening technique has been applied to this project. A combination between specific ligands, known by their efficiency to activate strong C−O bonds, and literature-based conditions has been designed for the chosen transformations. Using this strategy, two promising hits have been obtained using the same NHC ligand: a decarbonylative Suzuki-Miyaura and a decarbonylative borylation reaction.
13

Synthesis Of Ferrocenyl Substituted Pyrazoles By Sonogashira And Suzuki-miyaura Cross-coupling Reactions

Karabiyikoglu, Sedef 01 July 2010 (has links) (PDF)
Pyrazoles constitute one of the most important classes of heterocyclic compounds due to their interesting chemical and biochemical features. Researchers have studied many pyrazole containing structures for almost over a century in order to investigate the various biological activities possessed by these molecules. A new and important trend in these studies is to produce ferrocenyl substituted pyrazoles since ferrocene attracts considerable interest in the research field of organometallic and bioorganometallic chemistry because of its valuable chemical characteristics like high stability, low toxicity and enhanced redox properties. Moreover, the results of the studies focusing on ferrocenyl compounds have been quite promising. Therefore, the scope of this project involves the combination of the essential structural features of pyrazoles with a ferrocene moiety, which could provide new derivatives with enhanced biological activities. In the course of the project the synthesis of new pyrazole derivatives was performed through Sonogashira and Suzuki-Miyaura cross-coupling reactions of 5-ferrocenyl-4-iodo-1-phenyl-1H-pyrazole with terminal alkynes and boronic acids respectively in the presence of a catalytic amount of PdCl2(PPh3)2. Although Sonogashira and Suzuki-Miyaura coupling reactions are well known in literature, they were not studied in much detail with multi-substituted pyrazoles. This also revealed the requirement of the reinvestigation of the reactions and improvement of the yields of pyrazoles by optimizing the reaction conditions.
14

Coupling reactions using flow-generated diazo compounds

Poh, Jian Siang January 2017 (has links)
In recent years, the exploitation of flow technologies as an enabling tool to access unique chemical reactivity has flourished. This dissertation describes the utilisation of these flow methods to access new sets of highly versatile, unstable diazo compounds and their application in coupling reactions. In the first chapter, an introduction into the structure and reactivity of diazo compounds is provided, as well as a discussion of currently available methods for their generation. The second chapter describes the coupling of flow-generated, semi-stabilised diazo compounds with terminal alkynes for the synthesis of racemic di- and trisubstituted allenes, using copper(I) catalysis. The third chapter follows with an account of creating chiral disubstituted allenes by asymmetric coupling of flow-generated, semi-stabilised aryl aldehyde-derived diazo compounds with terminal alkynes, using a copper(I) catalyst and a newly developed pyridine(bisimidazoline) ligand. The fourth chapter describes the generation of new, highly reactive non-stabilised diazo compounds and their reaction with arylboronic acids to allow metal-free ‘protodeboronative’ and ‘oxidative’ C(sp2)-C(sp3) cross-couplings. Finally, the fifth chapter describes the experimental procedures relevant for the results described in Chapters 2-4.
15

Réactions médiées par l'acétate de manganèse (III) et pharmacochimie antiparasitaire

Tabélé, Clémence 21 September 2016 (has links)
La leishmaniose est une maladie infectieuse due à Leishmania, responsable de plus de 50 000 décès par an en ce qui concerne la forme viscérale (LV). La plupart des médicaments antileishmaniens se révèlent inefficaces (apparition de résistances avec la molécule de référence : la pentamidine) ou trop onéreux pour les patients (incidence principale en Inde). Il existe donc un réel besoin de nouveaux médicaments ne manifestant aucune résistance parasitaire, moins chers et administrables par voie orale. Dans cet objectif, plusieurs séries de monoamidoximes (de structure similaire à celle de la pentadimine) ont été synthétisées, en utilisant des réactions radicalaires médiées par l'acétate de manganèse (III), et sous irradiation micro-ondes. Des réactions pallado-catalysées ont permis de diversifier les structures obtenues : couplages de Suzuki-Miyaura et couplages originaux avec des dérivés de structure allyl alcool. Plusieurs amidoximes ont ainsi montré une bonne activité in vitro sur les formes promastigote et amastigote de Leishmania et une faible toxicité sur des lignées de macrophages, leur indice de sélectivité étant meilleur que celui de la pentamidine, utilisée comme référence. / Leishmaniasis is an infectious disease due to Leishmania : there are more than 50,000 deaths a year due to visceral form (VL). Most of antileishmanial drugs are either inefficient (too many resistances with the main drug : pentamidin) or too expensive for people (most of patients live in India). Thus, there is a real need for new drugs, without parasitical resistances, less expensive and orally administered. In this aim, several series of monoamidoxime, derivatives (pentamidine structure-like) have been synthesized using a free radical mechanism mediated by manganese (III) acetate under microwave irradiation. Palladium-catalyzed coupling reaction were also carried out for extensions of potential drugs : Suzuki-Miyaura reactions and original cross-coupling reactions involving allyl alcohol derivatives. Several amidoximes showed valuable in vitro activities toward Leishmania promastigote and amastigote forms,and low toxicity on macrophages, exhibiting a better selectivity index than pentamidine used as a drug compound reference.
16

Cross-Coupling Reactions in Flow Microreactor Systems / フローマイクロリアクターを用いたクロスカップリング反応

Moriwaki, Yuya 25 May 2015 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第19183号 / 工博第4060号 / 新制||工||1626(附属図書館) / 32175 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 吉田 潤一, 教授 杉野目 道紀, 教授 松原 誠二郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM
17

Towards Nickel Boride Catalyzed C-C Coupling Reactions / Nickelborid-katalyserade kopplingsreaktioner

Lakó, Ágnes January 2017 (has links)
This thesis focuses on the study of nickel boride as a catalyst in various coupling reactions. The nickel boride catalyst was investigated in three different coupling reactions, the experiments aimed at understanding the activity and catalytic properties of nickel boride. We successfully synthetized the nickel boride catalyst, alongside with the cobalt and iron boride. Different methods of preparation were compared and we concluded, that the differences in the preparation, such as solvent and atmosphere, influence the activity of the catalyst in coupling reactions. We found that the most suitable solvent for preparing nickel boride is anhydrous methanol, thus we proceeded our research with this catalyst. In the case of the Sonogashira cross-coupling we found that the homocoupling of the acetylene starting material is a side reaction we could not exclude. However, with the proper solvent it is possible to shift the reaction towards homocoupling, without the formation of the heterocoupling product. Thus, we decided to investigate the Glaser homocoupling between acetylenes. In the case of the Sonogashira coupling only TLC was used to examine the reaction mixture. However, in the case of Glaser coupling, after pre-investigations we developed a gas chromatography method for analyzing the reaction mixtures. We learned, that the homocoupling only results in trace amounts (2-4%) of product. Previous investigations in our research group showed, that the nickel boride could catalyze Suzuki-Miyaura-type couplings. Examining this reaction all three metal borides were tested; however, the reactions only led to the desired product with nickel boride. Analyzing the reaction with gas chromatography we learned that the choice of solvent influences the stability of the starting materials and the formation of side products. Reactions with different starting materials, in different solvents, with different bases were analyzed. The effect of microwave irradiation was also examined. Based on the results we concluded, that with nickel boride it is not possible to achieve high yields in coupling reactions.
18

silver-iron oxide particles as heterogeneous catalysts for the cross coupling of arenes and heterocycles

Qi Wang (14223956) 07 December 2022 (has links)
<p>Advances in nanomaterials research have stoked interests in the design of dispersible catalysts for specific organic transformations, with higher reaction efficiency or lower burden in post-reaction waste processing. Multicomponent heterogeneous catalysts generally offer higher catalytic performance than single-component catalysts, with metal–substrate interactions (MSI) playing a key role in their performance. This thesis focuses on silver–iron-oxide particles as heterogeneous catalysts, starting with a literature survey (Chapter 1) followed by the synthesis and catalytic properties of two novel types of Ag–Fe<sub>3</sub>O<sub>4</sub> particles that show strong potential for mediating C(sp<sup>2</sup>)–H arylation reactions (Chapters 2 and 3). Silver and especially iron oxide are much less expensive than other types of metals, and the magnetic properties of the Fe<sub>3</sub>O<sub>4</sub> support transferability and reuse of the active catalytic species which enables us to reduce the ratio of catalyst to reactant. These features address multiple goals outlined by the principles of green chemistry. The arylation of heterocyclic compounds is frequently used in the preparation of organic dyes, polymers, and pharmaceutical intermediates, and is a useful benchmark reaction for comparing our cross-coupling catalyst with those from prior reports. </p> <p>In Chapter 2, we describe the synthesis of colloidal silver–iron-oxide (SIO) and investigate its conversion into an efficient catalyst for C(sp<sup>2</sup>)–H arylation using novel modes of activation. This includes electrochemical activation using mild cathodic potentials, and photoactivation using a white light source. Both methods dramatically improve the efficacy of colloidal SIO as a catalyst for the cross coupling of diazonium salts with heteroaromatic rings at room temperature. High-resolution transmission electron microscopy analysis reveals that the SIO particles are primarily composed of colloidal Ag that are coated with nanosized islands of Fe<sub>3</sub>O<sub>4</sub>. The SIO catalysts are magnetically responsive and can be collected and reused multiple times, without requiring reactivation. The SIO is susceptible to acid degradation but can be preserved with neutralization by added base during reaction cycling. </p> <p>In Chapter 3, we describe a second-generation catalyst in which Fe<sub>3</sub>O<sub>4</sub> microspheres serves as the supporting substrate for Ag islands, with synthetic control over Ag size distribution. This material does not require any activation for cross-coupling catalysis, which can be attributed to better charge transfer between the Ag islands and Fe<sub>3</sub>O<sub>4</sub> substrate. A comparison of Ag–Fe<sub>3</sub>O<sub>4</sub> microspheres with different Ag/Fe ratios suggests that catalytic activity correlates with smaller particle sizes, where the strongest charge-transfer interactions are likely to occur. The role of MSI between Ag and Fe<sub>3</sub>O<sub>4</sub> was further explored using X-ray absorption spectroscopy. The second-generation Ag–Fe<sub>3</sub>O<sub>4</sub> catalysts are far more robust than the previous version and are better able to withstand acidic degradation, with less mass loss after multiple reaction cycles and no loss in catalytic function. Lastly, we have found that Ag–Fe<sub>3</sub>O<sub>4</sub> microspheres can also be an efficient catalyst for the reduction of nitro groups into amines, and describe progress toward the one-pot conversion of  nitroarenes into  cross-coupling products.  </p>
19

[en] ARYLOXY-SUBSTITUTED BENZOTHIADIAZOLE DERIVATIVES: A NEW CLASS OF ORGANIC EMITTERS FOR OLEDS / [pt] DERIVADOS DE BENZOTIADIAZOLA ARILÓXISUBSTITUÍDOS: UMA NOVA CLASSE DE EMISSORES ORGÂNICOS PARA OLEDS

ALESSANDRA PAZINI 07 October 2019 (has links)
[pt] O planejamento racional e a obtenção de novos compostos luminescentes com aplicações específicas continua sendo um importante desafio em síntese orgânica. Derivados do núcleo benzotiadiazola (BTD) com conjugação (Pi) estendida têm sido amplamente sintetizados e aplicados em diferentes aspectos da tecnologia da luz. Em geral, na estrutura desses derivados, grupos doadores de elétrons (D) são ligados ao anel BTD, que tem caráter aceptor de elétrons (A). Até o presente momento não haviam sido descritos derivados de BTD cuja porção doadora é um grupamento arilóxi. No presente trabalho foi desenvolvida uma rota sintética para derivados de BTD arilóxi-substituídos. Os compostos se mostraram altamente luminescentes em solução (Rendimento quântico de fluorescência de até 74 por cento) e com band gap adequado para aplicação em camadas emissoras de OLEDs. O desenvolvimento/otimização dos compostos foi dividido em duas partes. Na primeira parte, foram determinadas as condições reacionais para a obtenção dos novos derivados e foi avaliada qual a melhor configuração dos compostos: arilóxi-BTD aceptor ou arilóxi-BTD-doador. Um composto com característica arilóxi-BTD-doador se mostrou mais emissivo, assim, construiu-se um dispositivo OLED verde utilizando-o como camada emissora, como uma prova de conceito. Na segunda parte do trabalho, foi realizada uma otimização estrutural mais abrangente, onde oito novos derivados foram sintetizados e caracterizados. Através dessa nova otimização chegou-se no composto líder 4-(4-metoxifenóxi)-7-o-toluilbenzo[c][1,2,5]tiadiazol, que apresentou band gap eletroquímico de 3,2 eV, máximo de emissão em 471 nm (azul), emissão induzida por agregação e 83 por cento de rendimento quântico de fluorescência no estado sólido. A partir desse emissor puramente orgânico otimizado serão construídos novos dispositivos OLED. / [en] The rational planning and obtention of new luminescent compounds with specific applications can be considered an important challenge in organic synthesis. Benzothiadiazole (BTD) derivatives with extended (Pi) conjugation have been widely synthesized and applied in different aspects of light technology. In general, in the structure of these derivatives, electron donor groups (D) are bound to the BTD ring, which has electron acceptor character (A). To date, BTD derivatives in which the donor moiety is an aryloxy group have not been described. In the present work a synthetic route for aryloxy-substituted BTD derivatives has been developed. The compounds are highly luminescent in solution (Quantum fluorescence yield up to 74 percent) and display suitable band gaps for application as emitting layers in OLEDs. The development/optimization of the compounds was divided into two parts. In the first part, the reaction conditions were optimized and the best architecture of the compounds was evaluated: aryloxy-BTD-acceptor or aryloxy-BTD-donor. A compound with aryloxy-BTD-donor design displayed more intense emission, thus, a green OLED device was constructed using it as a emitting layer, as a proof of concept. In the second part of the work, a more comprehensive structural optimization was performed, and eight novel derivatives were synthesized and characterized. By means of this new optimization, the lead compound 4-(4- methoxyphenoxy)-7-o-tolylbenzo[c][1,2,5]thiadiazole was obtained, which showed an emission maximum at 471 nm (blue), band gap of 3,2 eV, aggregation emissioninduced and 83 percent of photoluminescence quantum yield in the solid state. This new leader compound will be explored as emissive layer in novel OLED devices.
20

Teluretos vinílicos em reações de acoplamento catalisadas por cloreto de paládio (II) ou complexos de níquel / Vinylic tellurides in coupling reactions catalized by palladium (II) chloride or nickel complexes

Raminelli, Cristiano 20 April 2005 (has links)
Nesta tese apresentamos um estudo sistemático da reação de alquinilação de teluretos Z-vinílicos promovida por PdCl2 e CuI. O sucesso de tal reação foi dependente da quantidade de PdCl2 empregado, por outro lado, o sal de cobre (I) não apresentou influência significativa sobre o curso da reação. Posteriormente, empregando PdCl2 em quantidades catalíticas, vários agentes oxidantes ou aditivos foram testados. No entanto, o resultado mais significativo foi obtido quando CuCl2 foi usado na presença de ar. Este resultado deu origem a uma nova metodologia para a alquinilação de teluretos Z-vinílicos, que emprega PdCl2 em quantidade catalítica e CuCl2 em excesso. Adicionalmente, um mecanismo para a reação desenvolvida foi proposto com base em experimentos realizados empregando espectroscopia de massas. Tendo em vista o alto custo dos reagentes de paládio, foram implementadas metodologias para promover a formação de ligações carbono-carbono, usando teluretos vinílicos e reagentes organometálicos na presença de quantidades catalíticas de complexos de níquel (II). Na última etapa do nosso trabalho, teluretos Z-vinílicos quirais foram sintetizados usando biocatálise como ferramenta, sendo posteriormente submetidos à reação de acoplamento resultando em álcoois enínicos de configuração Z quirais. A seqüência de reações foi testada inicialmente em sua versão racêmica. / In this thesis we report a systematic study concerning the alkynylation of Z-vinylic telurides promoted by PdCl2 and CuI. The performance of such reaction was dependent of the amount of PdCl2 employed. On the other hand, the copper (I) salt did not show significant influence in the course of the reaction. Afterwards, employing PdCl2 in catalytic amounts, several oxidizing agents or additives were tested. The most significant result was obtained when CuCl2 was used in the presence of air. This finding brought to light a new methodology for alkynylation of Z-vinylic telurides that employs catalytic amount of PdCl2 and CuCl2 excess. In addition, a mechanism for the new reaction has been proposed with basis in the data obtained by mass spectrometric experiments. In view of the high cost of the palladium reagents, we developed methodologies that promote the formation of carbon-carbon bonds by using vinylic tellurides and organometallic reagents in the presence of catalytic amounts of nickel (II) complexes. In the last stage of our work, chiral Z-vinylic tellurides were synthesized by using biocatalysis as a tool. After that, the chiral tellurides were submitted to the coupling reaction affording chiral enynic alcohos with Z configuration. The reaction sequence was tested initially in its racemic version.

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