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Blanchard, Angela N. "Investigations into the intramolecular geminal acylation reaction." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0015/MQ55484.pdf.
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Elliott, Christine E. "Exploiting the geminal acylation reaction to produce a ß-turn peptidomimetic." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2000. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape3/PQDD_0029/MQ62382.pdf.
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Hiault, Florence. "Biocatalyse : aldolisation, acylation et oxydation - Applications synthétiques." Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066515.
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Les travaux présentés dans ce manuscrit s’inscrivent dans le contexte général de l’essor de la biocatalyse et de son utilisation en synthèse organique. Le thème principal porte sur l’étude et le développement de différentes voies d’accès stéréosélectives à des acides alpha-aminés bêta-hydroxylés substitués. L’utilisation d’un biocatalyseur permettant d’accéder à des acides alpha-aminés bêta-hydroxylés par une aldolisation entre la glycine et divers aldéhydes, en présence de phosphate de pyridoxal, a été étudiée. Des aldéhydes aliphatiques, aromatiques et hétéroaromatiques ont pu être impliqués avec succès comme partenaires électrophiles dans ces réactions qui permettent un excellent contrôle de la configuration du carbone asymétrique créé en alpha du groupe carbonyle mais s’effectuent généralement avec des diastéréosélectivités plus modestes. Par ailleurs, un dédoublement cinétique enzymatique d’esters alpha,bêta-dihydroxylés, précurseurs d’acides alpha-aminés bêta-hydroxylés substitués en alpha, a été étudié. La méthode développée repose sur la monoacylation d’esters alpha,bêta-dihydroxylés, acycliques ou cycliques, en présence d’une lipase et d’un donneur d’acyle. De façon indépendante, la mise au point de séquences réactionnelles monotopes faisant intervenir une étape d’oxydation biocatalytique a été étudiée pour accéder à des composés aminés hautement fonctionnalisésThe research work presented in this manuscript pertains to the field of biocatalysis and some applications in organic synthesis. The main subject is the development of stereoselective synthetic methods allowing access to substituted alpha-amino beta-hydroxy acids. The use of a biocatalyst enabling the preparation of optically enriched alpha-amino beta-hydroxy acids in a single step from glycine by an aldol reaction, in the presence of pyridoxal phosphate, was investigated. Aliphatic, aromatic and heteroaromatic aldehydes could be successfully used as electrophilic partners in such reactions that allow an excellent control of the stereocenter created at the alpha position of the carbonyl group whereas moderate levels of diastereoselectivity were generally observed. The enzymatic kinetic resolution of acyclic or cyclic alpha,beta-dihydroxy esters, which are precursors of alpha-substituted alpha-amino beta-hydroxy acids, was also achieved by monoacylation in the presence of a lipase and an acyl donor. Independently, a one-pot sequence involving a biocatalytic oxidation was developed to access highly functionalized nitrogen containing compounds
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Mesas, Sánchez Laura. "Organocatalytic Acylation for the Kinetic Resolution of Secondary Aryl Alcohols : Synthetic Applications and Mechanistic Studies." Doctoral thesis, Uppsala universitet, Syntetisk organisk kemi, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-233734.
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The research described in this thesis focuses on the catalytic acylative kinetic resolution (KR) of aromatic secondary alcohols, using a planar-chiral 4-(dimethylamino)pyridine (DMAP) organocatalyst. In the first part of this thesis, the substrate scope of the above mentioned process was expanded to aromatic secondary alcohols that contain an extra functional group in the alkyl moiety, such as 1,2-azido alcohols, 2-hydroxy-2-aryl-ethylphosphonates and 2-hydroxy-2-aryl esters. Thus, the preparation of highly functionalized compounds in their enantiomerically pure form with excellent enantiomeric excess (up to 99% ee) was achieved. Furthermore, the synthetic applicability of this methodology was illustrated through the synthesis of two high value compounds, (R)-Pronethalol and (S)-3-hydroxy-N-methyl-3-phenylpropanamide, which is an immediate precursor of bioactive molecules such as (S)-Fluoxetine. The second part of this thesis deals with the mechanistic study of the acylative KR catalyzed by the planar-chiral DMAP derivative. Reaction Progress Kinetic Analysis methodology was used in the investigation of the reaction mechanism, probing that no notable product inhibition or decomposition of the catalyst occurs in the studied system. The reaction rate showed fractional order dependence on the concentration of both reactants. Furthermore, NMR spectroscopy was utilized to study the equilibrium between the different catalyst states, which explains the measured kinetics of the reaction.
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Melanson, Rhea Lise. "Examination of the geminal acylation reaction and its application towards the synthesis of a steroid backbone." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/MQ62399.pdf.
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Balaguer, Amanda Marie. "Routes to Acylated Sydnone Esters." Wright State University / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=wright1316529382.
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Zeytinci, Serhat. "Synthesis Of Ferrocenyl Substituted Aziridines." Master's thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/12607285/index.pdf.
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A new method for the efficient synthesis of ferrocenylenones was developed. Acryloyl, methacryloyl, crotonyl, cinnamoyl, and β
-methylcrotonyl chlorides reacted with ferrocene in the presence of a Lewis acid (EtAlCl2 or EtAlCl2-Me3Al) to give the corrosponding ferrocenylenones (acryloyl, methacryloyl, crotonyl, cinnamoyl, and &
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-methylcrotonylferrocenes) in good isolated yields. Using the Gabriel-Cromwell reaction, acryloyl and crotonoylferrocenes were converted to the novel ferrocenyl substituted aziridines with benzylamine, isopropylamine and furfurylamine. The aziridines were isolated in good to excellent yields.
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Gali, Meghanath. "Synthesis of Small Molecule Inhibitors of Janus Kinase 2, Phosphodiesterase IV, GABAA and NMDA receptors: Investigation of Mcmurry, Mannich and Chemoenzymatic Strategies." Scholar Commons, 2011. http://scholarcommons.usf.edu/etd/3110.
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Stilbenoids possess a wide range of biological properties such as, anticancer, antiplatelet aggregation, antiestrogenic, antibacterial, antifungal and antiatherogenic, etc. Owing to these therapeutic values, a great deal of attention attracted in the synthesis of derivatives of stilbenes. During the course of the study, G6 a novel stilbenoid was discovered, through high throughput screening, to be a potent inhibitor of mutated JAK2-V617F. The mutated JAK2 variant has been implicated in various myeloproliferative disorders (MPDs) including polycythemia vera (PV), essential thrombocythemia (ET) and primary myelofibrosis (PMF) has been targeted by therapeutics. Chapter 2 describes the synthesis of analogs of the stilbenoid G6 and N-substituted stilbenes bisoxazines by utilizing Mcmurry reaction and Mannich condensation methods. The main emphasis of this work is to develop novel stilbenoids as inhibitors of JAK2-V617F mutated Jak2 enzyme in Human erythroleukemia cells (HEL) since this mutation is discovered in the majority of patients with myeloproliferative disorders (MPDs). Using Mcmurry reaction, five novel trans-hydroxystilbenes have been synthesized from carbonyl compounds. Subsequently using Mannich coupling with five secondary amines and five primary amines, 25 novel stilbenoids and 9 novel N-substituted stilbene bisoxazines have been synthesized. In HEL cell assay, 8 stilbenoid analogues have been identified as potent inhibitors of Jak2 enzyme.
Chapter 3 describes the modification of ketamine structurally for the synthesis of novel analogues to study for their agonist activity at GABAA receptors and antagonist activity at NMDA receptors. Ligand gated ion channels like GABAA and NMDA receptors are membrane-embedded proteins at synaptic cleft which controls intercommunication among neurons and plays an important role in motor control activity, learning. GABAA receptors are responsible for inhibitory action potentials while NMDA receptors are responsible for excitory action potentials. Ketamine, known as dissociative anesthetic, produces profound analgesia at low doses to a unique cardiovascular stimulation and a cataleptic state at higher doses with dose dependent side effects like vivid dreams, disruptions of cognitive functions. The main emphasis of this work is the synthesis of novel analogues of ketamine by transforming carbonyl group in ketamine to imine functionality with small to bulkier groups and to identify an analogue of ketamine which is highly potent in its activity at the both GABAA and NMDA receptors and improved clinical actions. Studies of analogues activity against GABAA subtypes α6Β2δ, α1Β2γ2 receptors and NMDA subtypes NR1/2A, NR1/2B, NR1/2D receptors have been described.
Chapter 4 describes the formal synthesis of (±)-Rolipram and the chemoenzymatic synthesis of -aryl--lactone, a Rolipram analogue. The key steps, Pd catalyzed arylation of diethylmalonate and the efficient use of selective acylation of 1, 3-diol entails the formal synthesis of (±)-Rolipram. The regioselective deacylation of Β-aryl-1, 4-diacetate by lipase Pseudomonas Sepacia entails the formation of Β-aryl-γ-lactone. The efficient use of various methods including halogen exchange, Heck arylation of diethylmaleate and lactonization for the synthesis of Β-aryl-γ-lactone have been discussed. The present work provides an efficient and general route to γ-lactones.
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Wakeham, Russ. "Environmentally benign acylation reactions." Thesis, University of Bath, 2014. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.642048.
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This thesis outlines the work carried out in the last three and half years concerning the development of environmentally benign acylation reactions and determination of the range of these reactions through substrate screening and investigations into the mechanisms by which they are operating.
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CASTANY, MARIE-HELENE. "Les triflates du germanium en synthese organometallique et organique." Toulouse 3, 1998. http://www.theses.fr/1998TOU30267.
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Cette these presente la synthese et la reactivite de triflates du germanium en tant qu'agents de germylation et catalyseur acide de lewis. Le premier chapitre decrit plusieurs voies de synthese de mono- et ditriflates du germanium par action de l'acide triflique sur differents composes organomettaliques. Le deuxieme chapitre est consacre a la germylation de nombreuses fonctions organiques a partir des triflates du germanium ou de chlorogermanes. Pour ces deux voies de synthese, une etude mecanistique est menee afin d'interpreter la regiochimie et la stereochimie de la germylation. Le troisieme chapitre met en evidence l'activite catalytique des triflates germanies en tant qu'acide de lewis dans la reaction d'aldolisation croisee entre les enols o- et c- germanies et un aldehyde, un acetal ou une imine. La diastereoselectivite observee pour ces reactions a pu etre interpretee a partir d'un mecanisme d'approche a interactions steriques et electrostatiques minimales faisant intervenir des etats de transitions ouverts ou cycliques. La reaction de friedel et crafts, sous catalyse par le triflate de trimethylgermanium, fait l'objet du dernier chapitre.
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Rahemtulla, Benjamin F. "Development of cation-directed acylation reactions." Thesis, University of Oxford, 2018. http://ora.ox.ac.uk/objects/uuid:06bfa464-4c5c-47d7-a35c-9cf60576dec4.
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This thesis describes work conducted towards the enantioselective acylation of ketones using phase-transfer catalysis. Chapter 1 introduces the field of ketone acylation, with a focus on catalytic methods accompanied by the generation of axes, planes or points of chirality during these transformations. Chapters 2 describes the synthesis and evaluation of a variety of different frameworks for enantioselective ketone O-acylation; we highlight the selectivity and reactivity challenges faced when attempting this transformation (Scheme I). Chapter 3 focuses on the intramolecular O-acylation of enolates to generate axially chiral lactones. The development of these systems led to the discovery that the C/O-selectivity of this reaction was dependent on the steric hindrance about the axis of rotation, and C-acylation could be favoured under the correct conditions. Chapter 4 describes the conception and development of an enantioselective C-acylation reaction, culminating in the first reported catalytic enantioselective direct C-acylation of a ketone (Scheme II). The scope and limitations of this methodology were investigated and the products were successfully elaborated to afford a range of spirocyclic architectures. Finally, chapter 5 focuses on the kinetic analysis of the enantioselective C-acylation reaction in order to increase our understanding of the mechanisms behind phase-transfer catalysis and the mode of activation of the catalyst.
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Jayne, A. J. "Friedel-Crafts acylation reactions catalysed by solids." Thesis, Swansea University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.637410.
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The various inorganic solids that may be employed as heterogeneous catalysts in organic reactions are discussed in Chapter 1. In the present climate, heterogeneous catalysts are seen as more environmentally acceptable alternatives to homogeneous Lewis acid type catalysts. Chapter 2 describes the Friedel-Crafts acylation of aromatics. Discussion focuses on both the classical and solid catalysed reactions. The study of a pharmaceutical intermediate is described in Chapter 3. The aims of the work described were to develop an efficient and commercially viable process for the production of 1-(4-methoxyphenyl)-2-phenyl-1-butanone by the acylation of anisole over a suitable heterogeneous catalyst. In Part A of Chapter 4, the acetylation of a range of 1,2-disubstituted aromatics over solids is discussed. Part B describes the use of different anhydrides in the acylation of 2,3-dihydrobenzofuran over a number of solids to elucidate the generality of the reaction. Investigations show the influence of the solid catalyst and the effective recovery and regeneration of a zeolite catalyst. Finally, the acylation of 2,3-dihydrobenzofuran with ethyl oxalyl chloride over heterogeneous catalysts is described in Chapter 5. The reaction proved difficult with close consideration given to the reasoning behind the poor performance of the reaction; a good case in point being the amount of material unaccounted for in certain experiments. Investigations led to the isolation and characterisation of what were considered to be likely by-products of the reaction. Efforts were made to reduce the likelihood of such by-products being formed and with further attention, a yield of 73% of the corresponding para acylated product was formed in the presence of zeolite Hβ after 7 days. Having speculated that the difficulties encountered during the study of this reaction may lie with the nature of the acylating agent, the use of mixed anhydrides based on ethyl oxalyl chloride as potential acylating agents was investigated.
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Hudson, Peter. "Studies of ionic and radical acylation reactions." Thesis, University of Nottingham, 1991. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334795.
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Eck, Geneviève. "Synthèse partielle de la frédéricamycine A." Paris 6, 1986. http://www.theses.fr/1986PA066466.
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Le but du travail a été la synthèse d'un composé spirannique dicétonique modèle : le spiro (indane)-1,2'-(dimethoxy-4',7'indanedione-1',3')1. La première voie envisagée s'inspire de la synthèse de dialkyl-2,2 indanediones-1,3 par double réaction de Friedel-Crafts entre le dimethoxy-1,4 benzène et un chlorure d'acide dialkyl malonique. Ainsi, dans un premier temps le dimethoxy-1,4 benzène et l'acide cyclopentane dicarboxylique-1,1, en présence du réactif acide méthanesulfonique-anhydrique, fournissent le composé spirannique dicetonique résultat d'une double condensation avec un rendement de 45% : le spiro (dimethoxy)4,7 indanedione-1,3)-2, l'-(cyclopentane). La même réaction entre le dimethoxy-1,4 benzène et l'acide indane dicarboxylique-1,1 donne le composé 1 modèle avec un rendement de 8%. La deuxième voie étudiée a été la synthèse avec un rendement de 27% spiro (indane)-1,2'-(dimethoxy-4'7') 2 par alkylation du carbethoxy-1 indane par le chloromethyl-1 dimethoxy-2,5 benzène, saponification puis cyclisation par acylation intramoléculaire du produit obtenu. La transformation du compose monocétonique 2 en composé dicétonique 1 se fait par oxydation de la position benzylique avec un rendement de 8%. La derniere methode de construction de la structure spirannique de la frédéricamycine A a été la synthèse du spiro (indane)-1,1'-(cyclopentene-3'one-2') 3 par acylation desilylation du compose resultant de la saponification du produit d'alkylation du carbechoxy-1 indane par le (chloro-3 propenyl-1) trimethylsilane. Le produit 3 constituerait un accepteur de Michael pour une réaction de Hauser avec une phenylsulfonyl-3 isobenzofuranone-1 (3h) et fournirait ainsi un compose naphtoquinonique semblable à la frédéricamycine A.
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Onobun, Emmanuel. "A Novel Method for Synthesis of Hydroxytyrosol." Digital Commons @ East Tennessee State University, 2017. https://dc.etsu.edu/etd/3267.
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Hydroxytyrosol, 3,4-dihydroxyphenolethanol, a naturally occurring polyphenol most common in olive tree (Olea europaea), is one of the most effective member of the polyphenols family, because of its remarkable antioxidant activity, its ability to inhibit oxidation of low density lipids (LDL), and its protection against DNA oxidative damage. Hydroxytyrosol, which is widely used in cosmetics and food supplements industries, can be purchased as an olive oil extract that contains low concentration of hydroxytyrosol besides other polyphenols. The price and low natural abundance of hydroxytyrosol make alternative synthetic sources very attractive. In this research, a novel method for the synthesis of pure hydroxytyrosol from a commercially inexpensive precursor catechol was developed; this can satisfy the increasing market demand and provide a more economical alternative source for this valuable polyphenol.
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Silva, Bruno Henrique Sacoman Torquato da. "Estudos sobre a utilização do pentacloreto de Nióbio, como ácido de Lewis, em reações de acilação de Friedel-Crafts, visando à síntese de compostos com potencial aplicação como corantes sensibilizadores /." Bauru, 2018. http://hdl.handle.net/11449/153383.
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Orientador: Luiz Carlos da Silva FilhoResumo: A reação de acilação de Friedel-Crafts é uma das mais importantes reações de formação de ligações carbono-carbono em compostos aromáticos. As reações de acilação de Friedel-Crafts ocorrem basicamente por meio da reação entre compostos aromáticos com haletos de acila ou anidridos na presença de um ácido de Lewis. Assim, neste trabalho foi estudado o uso do pentacloreto de nióbio como ácido de Lewis nas reações de acilação de Friedel-Crafts visando à síntese de corantes sensibilizadores. Os derivados de fluoresceína foram sintetizados a partir de derivados fenólicos e derivados de anidrido, na presença de NbCl5 e sob aquecimento. Os produtos de interesse foram obtidos com rendimentos de 54 a 90% e em curtos tempos reacionais que variaram de 50 a 200 minutos. As fluoresceínas apresentaram absorção e emissão de luz dentro do comprimento de onda do visível, com alta intensidade e altos valores de rendimento quântico de fluorescência (0,60 a 0,93) quando dissolvidos em soluções alcalinas. Os derivados de fluoresceínas foram aplicados na confecção de células solares de Gratzel apresentando eficiências de conversão que variaram de 0,11 a 0,23%. Também foi estudado a aplicação dos derivados de fluoresceínas como corantes iniciadores em reações de fotopolimerização de resinas de dimetacrilato. Estas resinas tem sido largamente utilizadas na odontologia, devido as suas propriedades como baixa toxicidade, baixa solubilidade em água e alta resistência mecânica. As fluoresceínas promoveram... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The Friedel-Crafts acylation reaction is one of the most important reactions for the formation of carbon-carbon bonds. The Fridel-Crafts acylation reaction occurs basically by a reaction between aromatic compounds with acyl halides or anhydrides in the presence of a Lewis acid. Thus, in this work it was studied the use of niobium pentachloride as Lewis acid in Friedel-Crafts acylation reaction, aiming the synthesis of sensitizing dyes. The fluorescein derivatives were synthesized from phenolic derivatives and anhydride derivatives, in the presence of NbCl5 and under heating. The products of interest where obtained in yields of 54 to 90% and in short reaction times ranging from 50 to 200 minutes. The fluorescein derivatives presented absorption and emission within the range of visible and with high intensity and high fluorescence quantum yield (0,60 to 0,93) when dissolved in alkaline pH. Due to these good results obtained in the photophysical study, the fluorescein derivatives were applied in Gratzel solar cells, presenting convertion efficiencies that ranging from 0.11 to 0.23%. It has also been studied the application of fluorescein derivatives as initiator dyes in photopolymerization reactions of dimethacrylated resins. This resins have been widely used in dentistry, due this properties as, low toxicity, low solubility in water and high mechanical resistance. The fluoresceins promoted the photopolymerization of dimethacrylated resins with conversion values ranging from 1.2... (Complete abstract click electronic access below)
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Brown, Audra Denise. "α-aminoalkylphosphonate di(chlorophenyl) esters as inhibitors of serine proteases : Part II: A kinetic study of the coupling of the hydrolysis product of the N-tosylalanine ester of 5-phenyl-3-hydroxypyrrole to various diazonium salts : Part III: Rates of thrombin acylation and deacylaton upon reaction with low molecular weight acylating agents, carbamylating agents and carbonylati." Thesis, Georgia Institute of Technology, 1994. http://hdl.handle.net/1853/27552.
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Zhang, Wanying. "A Mechanistic Approach Towards the Discovery of Catalytic Acylation Reactions." Thesis, Université d'Ottawa / University of Ottawa, 2017. http://hdl.handle.net/10393/35646.
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The development of new, efficient methods for the formation of carbon-carbon bonds using transition metal catalysis has broad applications in the field of organic chemistry and is the key to efficient chemical synthesis. Many efforts had been made to develop efficient ways to make these linkages particularly with the aid of metals such as Rh, Pd, Ni, Ru and Cu. Our group is primarily focused on exploring how these transition metals can activate typically inert functional groups, paving way to new synthetic routes to construct more complex molecules.
Chapter 1 describes attempts that were conducted to achieve hydroacylation between an aldehyde and a non-conjugated alkene via a metal hydride intermediate. The use of RuHCl(CO)(PPh3)3 proved to be the most efficient catalyst for this transformation thus far. Mechanistic investigations were conducted to explore different possibilities to enable this transformation. This chapter also identifies a new self-aldol domino reaction, which consists of a self-aldol condensation of an aldehyde, followed by oxidation and decarbonylation giving rise to a ketone product. Finally, the use of a simple and direct method to access deuterated aldehydes using RuHCl(CO)(PPh3)3 as a catalyst and D2O as a deuterium source is outlined.
Chapter 2 describes a novel Suzuki-Miyaura system that couples esters and boronic esters to form the corresponding ketone product. It was found that an NHC-based Pd catalyst is crucial in the transformation wherein it activates the C(acyl)-O bond of the ester. It is notable that this transformation takes place with the absence of decarbonylation. Reactivity under water in the presence of surfactants was also discovered. Results in aqueous media were demonstrated to be milder than in organic conditions, while achieving similar yields. This system was also applied to coupling of esters and anilines.
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Simon, Meike [Verfasser], and Paul [Akademischer Betreuer] Knochel. "Diastereoselective intramolecular carbolithiation and acylation reactions / Meike Simon ; Betreuer: Paul Knochel." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2018. http://d-nb.info/120987797X/34.
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Gardner, June Ann. "Friedel-Crafts acylation reactions using heterogeneous catalysts stimulated by microwave radiation." Thesis, University of Central Lancashire, 2004. http://clok.uclan.ac.uk/20208/.
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Ion exchanged zeolites, ion exchanged clays, sulphated zirconia and silica supported phosphotungstic acid were prepared. Characterisation of the catalysts using pyridine adsorption revealed the catalysts contained both Brønsted and Lewis acid sites. When the catalytic activities for the acylation of toluene and anisole were studied there was found to be a correlation between the Brønsted acidity and the catalytic activity. The reactivity of the catalysts is dependant upon both the concentration and the chain length of the carboxylic acid. An optimum chain length being in the range Cm-C12. An aromatic:carboxylic molar ratio of 30: I was demonstrated to be preferable to either 300:1 or 3:1. The activation energies for the acylation of toluene were determined to be in the range 165-359 ki mol' and those for anisole 67-196 kJ mor 1 . Microwave experiments were performed in both batch and flow reactors. Under both reactor configurations microwave stimulation gave consistent increases in catalyst activity. Attempts were made to correlate this with the material dielectric properties, unfortunately, no correlation was found. Under the high E-field conditions Of the single mode (flow reactor) only the zeolites proved to be sufficiently robust as to provide any meaningful data. These catalysts displayed an increased selectivity to the ortho-isomer which was maximised when hexanoic acid was used as the acylating agent. The selectivity to the ortho-isomer increased with increasing microwave power.
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Motion, Keith Robert. "Cyclisation reactions of α,β,γ,δ-unsaturated nitrile ylides and acylation reactions of 2,3-benzodiazepines." Thesis, University of Edinburgh, 1986. http://hdl.handle.net/1842/12120.
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Laidlaw, Paul. "Catalysis of organic reactions by cation-exchanged zeolites." Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366734.
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Larionov, Evgeny. "Activity and selectivity of DMAP derivatives in acylation reactions: experimental and theoretical studies." Diss., lmu, 2011. http://nbn-resolving.de/urn:nbn:de:bvb:19-131192.
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Guo, Hua. "Synthesis and selected reactions of 2-alkenylthiazolines." Master's thesis, Mississippi State : Mississippi State University, 2008. http://library.msstate.edu/etd/show.asp?etd=etd-07082008-100959.
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BONNET, DOMINIQUE. "Nouvelles strategies de synthese d'hydrazinopeptides sur support solide et application a l'obtention de lipopeptides par reactions chimioselectives." Lille 2, 2000. http://www.theses.fr/2000LIL2P263.
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Grokenberger, Lucie [Verfasser], and Paul [Akademischer Betreuer] Knochel. "Cobalt-catalyzed cross-couplings and acylation reactions using organozinc reagents / Lucie Grokenberger ; Betreuer: Paul Knochel." München : Universitätsbibliothek der Ludwig-Maximilians-Universität, 2020. http://d-nb.info/1214180361/34.
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Edoo, Zainab. "Mechanism of L,D-transpeptidase inhibition by β-lactams and diazabicyclooctanes." Electronic Thesis or Diss., Sorbonne université, 2019. https://accesdistant.sorbonne-universite.fr/login?url=https://theses-intra.sorbonne-universite.fr/2019SORUS565.pdf.
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La résistance aux antibiotiques est une menace mondiale qui conduit à un besoin urgent de développement de nouveaux antibiotiques. L'étude du mécanisme d'inhibition des cibles des antibiotiques est cruciale pour le développement de nouvelles molécules. Le caractère essentiel du peptidoglycane, le composant majeur de la paroi bactérienne, ainsi que soixante-dix ans d'utilisation des β-lactamines ont fait de la polymérisation du peptidoglycane une cible attractive et validée pour les antibiotiques. Les protéines de liaison à la pénicilline (PLP) ont longtemps été considérées comme les seules enzymes catalysant l’étape essentielle de réticulation du peptidoglycane. La thèse explore l'inhibition d'une famille distincte d'enzymes, les L,D-transpeptidases (LDT), qui jouent un rôle prépondérant dans la réticulation chez Mycobacterium tuberculosis. Nous avons montré que l'efficacité d'inhibition des LDT par les β-lactamines est principalement régie par la réactivité du noyau β-lactame. Nous proposons que l'acylation des LDT par les β-lactamines implique la formation d'un intermédiaire, une amine anionique, suivie d'une étape irréversible qui est essentielle pour l'activité antibactérienne. Une approche par spectroscopie de fluorescence a été développée pour explorer les mécanismes d'inactivation et évaluer l'efficacité de nouvelles molécules. Nous avons également identifié une nouvelle famille de molécules, les diazabicyclooctanes (DBO), qui inactivent les LDT par la formation d'un thio-carbamoyl-enzyme. Nous discutons de plusieurs stratégies basées sur le mécanisme d’inactivation pour l’optimisation rationnelle d’inhibiteurs appartenant aux familles des β-lactamines et des DBOAntibiotic resistance is a growing and global threat to human health that has led to an acute need for the development of new antibiotics. Elucidating the mechanism of inhibition of antibiotic targets is crucial for the development of more potent drugs. The essentiality of peptidoglycan and more than seventy years of successful use of β-lactams have made polymerization of this major cell wall component an attractive and validated target for drug development. Active-site serine Penicillin-Binding Proteins (PBPs) have long been considered as the only enzymes catalyzing the essential cross-linking step of peptidoglycan polymerization. The thesis explores inhibition of a distinct family of enzymes, the active-site cysteine L,D-transpeptidases (LDTs), that have a preponderant role in peptidoglycan synthesis in Mycobacterium tuberculosis. We show that the efficacy of LDT inhibition by β-lactams is primarily governed by the reactivity of the four-membered ring. We propose that acylation of LDTs by β-lactams proceeds through formation of an amine anion intermediate, followed by a subsequent irreversible step that is essential for the antibacterial activity of the drugs. A fluorescence spectroscopy approach enabling kinetic analyses of the acylation steps was developed to explore inactivation mechanisms and to evaluate the efficacy of new synthetic drugs. We also identify diazabicyclooctanes (DBOs) as new pharmacophores that inactivate LDTs by formation of a thio-carbamoyl-enzyme. We discuss several mechanism-based strategies for rational optimization of LDT inhibitors belonging to the β-lactam and DBO families
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Aribert, Nicolas. "Acylation hétérogène de Friedel-Crafts en milieu CO2 supercritique." Phd thesis, Toulouse, INPT, 2009. http://oatao.univ-toulouse.fr/16222/1/aribert.pdf.
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L’acylation de Friedel-Crafts est parmi les réactions les plus fondamentales et les plus utiles pour former des cétones aromatiques. Bien que la mise en oeuvre de ces réactions soit habituellement pénalisante en termes de sous produits formés, de rendement atomique et de quantité de catalyseur utilisée, cette voie est encore largement utilisée dans l’industrie de la chimie fine. Ces dernières années, la prise de conscience de l’impact des activités industrielles sur l’environnement a mené les chimistes à travailler sur de nouvelles voies, moins dangereuses et plus respectueuses de l’environnement.Nous avons considéré ici l’acylation d’un dérivé du benzofurane par un chlorure d’acyle, correspondant à une étape intermédiaire pour la fabrication d’un principe actif pharmaceutique. Dans cette étude, la première proposition a consisté à remplacer les catalyseurs classiques (FeCl3 ou AlCl3) par des catalyseurs solides réutilisables. Dans ce travail, plusieurs catalyseurs (zéolites, résines échangeuses d’ions...) ont d’abord été testés dans des conditions « conventionnelles » , c’est-à-dire en utilisant un solvant organique, afin de déterminer le plus performant, en termes de réactivité, de durée de vie et de réutilisabilité. Une zéolite Y s’est avéré la plus adaptée. Cependant, l’utilisation d’un solvant organique (ici le 1,2-dichlorobenzène) reste discutable et l’utilisation du CO2 supercritique comme solvant a donc été envisagée. Pour cela, nous avons imaginé et dimensionné un réacteur tubulaire à lit fixe de catalyseur fonctionnant sous pression et en continu. Les résultats présentés montrent la faisabilité d’un tel procédé et pose les jalons pour arriver à une ou des solutions pour une meilleure mise en oeuvre industrielle des réactions de Friedel-Crafts.
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NASS, OLIVIER. "Syntheses et reactions de complexes spiraniques de dienes fer-tricarbonyle : acylation intramoleculaire de friedel-crafts et cyclocarbonylation." Université Louis Pasteur (Strasbourg) (1971-2008), 1997. http://www.theses.fr/1997STR13230.
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La decomplexation avec carbonylation de dienes fer tricarbonyle 1,1,3-trisubstitues a ete reexaminee en vue d'un acces stereocontrole a des sesquiterpenes spiro4. 5decaniques. Les complexes precurseurs ont ete prepares par homologation de cyclohexanones par transposition de meyer-schuster, conversion en dienes exocycliques et complexation diastereoselective. L'etude de cette cycloaddition 4+1 formelle a permis de verifier sa stereospecificite, l'accessibilite de cyclopenten-2-ones spirobicycliques et tricycliques, et de preciser les possibilites et limites d'ordre sterique du procede. L'acylation intramoleculaire de friedel-crafts, inedite pour ces complexes de fer, a d'autre part ete examinee au depart de derives dieniques substitues en position 1 par un residu carboxyalkyle. Apres optimisation, les cycles a 5 et 6 carbonnes ont ete formes avec des rendements respectifs de 75 et 55%. Un acces simple et rapide a des complexes de 2h-pyrannes bicycliques inedits, analogues heterocycliques des cyclohexadienes fer tricarbonyle, a par ailleurs ete mis en evidence. Un important potentiel synthetique est envisageable pour ces composes. Une reflexion a ete engagee sur l'interet general de la sous-structure diene fer tricarbonyle en tant que groupement stereodirecteur. La synthese de complexes optiquement purs par complexation diastereoselective, et la modification stereoselective de cetones et d'alcools au voisinage immediat du site de coordination ont ete analyses, documentes et illustres par des exemples concrets. Ce memoire revele les caracteristiques reactionnelles et structurales inhabituelles des complexes de dienes exocycliques prepares. Il est d'autre part illustratif de divers concepts stereochimiques, de l'incidence des ruptures de symetrie sur le deroulement d'une reaction, et de l'interet particulier des composes meso et de la notion de pseudoasymetrie.
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Kheirabadi, Mahboubeh. "Inside-out design and synthesis of spiroligomers for transesterification reactions." Diss., Temple University Libraries, 2014. http://cdm16002.contentdm.oclc.org/cdm/ref/collection/p245801coll10/id/304046.
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ChemistryPh.D.
This work describes the application of spiroligomers as serine hydrolases mimetics. Through collaboration with Kendall Houk's group, for the first time in the Schafmeister lab, we demonstrate that "theozymes" can be successfully used as models to design highly functionalized spiroligomer constructs for organocatalysis. We demonstrate a structure-function relationship between the structure of a series of bi-functional and tri-functional spiroligomer based transesterification catalysts and their catalytic activity. First, we designed and synthesized a series of stereochemically and regiochemically diverse bi-functional spiroligozymes to identify the best arrangement of a pyridine as a general base catalyst and an alcohol nucleophile to accelerate attack on vinyl trifluoroacetate as an electrophile. The best bifunctional spiroligozyme reacts with vinyl trifluoroacetate to form an acyl-spiroligozyme conjugate 2.7x103-fold faster than the background reaction with benzyl alcohol. We then incorporated an additional urea functional group to activate the acyl-spiroligozyme intermediate through hydrogen bonds and enable acyl transfer to methanol. The best trifunctional spiroligozyme carries out multiple turnovers and acts as a transesterification catalyst with k1/kuncat of 2.2x103 and k2/kuncat of 1.3x102. Quantum mechanical calculations identified four transition states in the catalytic cycle and provided a detailed view of every stage of the transesterification reaction. With the aim of accelerating the k2, we sought to design better oxyanion holes that hold multiple hydrogen bonding groups in close proximity of the catalytic groups. A macrocyclic motif would be a good candidate to force the oxyanion hole arm to arrange hydrogen-bonding groups in a precise three-dimensional constellation for transition state stabilization. In Chapter 4, we introduce an in silico designed macrocyclic spiroligomer, which overlays well with catalytic active site of an inhibitor bound-esterase. Finally, we detail our effort to develop new methodologies for rapidly synthesizing spiroligomers on solid-support. This would allow us to efficiently permute their structures for diverse applications such as organocatalysts, host molecules, and biologically related applications such as inhibiting protein-protein interactions.
Temple University--Theses
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Olivon, Kevin. "Procédés catalytiques et outils millifluidiques : applications aux réactions de Friedel-Crafts et d'oxydation." Thesis, Bordeaux, 2014. http://www.theses.fr/2014BORD0143.
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La recherche de nouvelles méthodes pour l’acquisition de données physiques et chimiques de réactions en limitant les effet néfastes sur l’Homme est d’une grande importance pour la chimie moderne. L’utilisation de nouveaux outils miniaturisés permet de limiter les quantités de produits chimiques utilisées tout en augmentant la productivité de la recherche. En effet, l’étude de différents paramètres contrôlés simultanément permet d’augmenter le nombre d’expériences pour un temps donné. Malgré tout, cette étape doit être réalisée après détermination au préalable des paramètres clés de la réaction par l’utilisation d’outils haut débit tels que la robotique. Cesdifférents outils sont utilisés pour l’optimisation et la recherche d’une nouvelle voie de synthèse d’une réaction d’intérêt industriel.De plus, pour répondre à l’intérêt de la catalyse hétérogène dans l’industrie pour la séparation facilitée et le recyclage de ces catalyseurs, nous avons développé deux outils miniaturisés. Cesderniers permettent l’étude et l’acquisition de données de réactions chimiques catalysées par des solides. Le développement s’est inscrit en deux étapes : une caractérisation physique des outils puis l’étude d’une réaction modèle industrielle, l’acylation de l’anisole par des catalyseurs de type zéoliteThe search for new methods for the acquisition of physical and chemical reactions by limiting the effect on humans is of great importance for modern chemistry. The use of new miniaturized tools can limit the quantities of chemicals used while increasing research productivity. Indeed, the study of the various parameters monitored simultaneously increases the number of experimentsfor a given time. Nevertheless, this step must be performed after prior determination ofthe key parameters of the reaction by the use of high flow tools such as robotics. These tools are used for optimization and the search for new synthetic pathway of a reaction of industrial interest. In addition, to meet the interests of heterogeneous catalysis in industry for easier separation and recycling of these catalysts, we have developed two miniaturized tools. These allow the study and data acquisition of chemical reactions catalyzed by solid. Development was registeredin two stages : a physical characterization tools and the study of an industrial model reaction, the acylation of anisole with zeolite catalysts
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Zine, Khalid. "Synthèse régio- et stéréosélective du 4,4,4-trifluorobut-2-énoate d'éthyle porteur d'un groupement tributylstannyl en position alpha ou bêta : réactivité cupro-catalysée des vinylétains en l'absence de complexes du palladium." Thesis, Tours, 2011. http://www.theses.fr/2011TOUR4044/document.
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Vu l’importance des molécules fluorées dans différents domaines et vu la réactivité engendrée par le 4,4,4-trifluorobut-2-ynoate d’éthyle 1 lors des travaux antérieurs réalisés au laboratoire, nous avons décidé d’étudier le comportement de dérivé fluoré 1 vis-à-vis d’hydrure tributylétain sans l’emploi de catalyseurs ou d’additifs. Le but est d’accéder à de nouveaux synthons fluorés par voies originales.Après une étude préliminaire pour effectuer cette réaction d’hydrostannation dans les meilleures conditions, nous avons réalisé pour la première fois la synthèse totalement régio- et stéréosélective des vinylétains (Z)-2α et (Z)-2β par un simple choix de solvant et sans l’utilisation d’aucun additif. Ces résultats inédits et très encourageants, nous ont conduis à étendre cette stratégie à d’autres hydrures comme l’hydrure de diphénylphosphine et l’hydrure de triphénylgermane..Les vinylétains (Z)-2α et (Z)-2β- de configurations bien définies sont des réactifs de choix pour élaborer de nouvelles structures fonctionnelles trifluorométhylées. En effet, le couplage cupro-catalysé de ces vinylétains en présence d’une quantité catalytique de CuI (10 moles%) avec une variété de bromures d’allyles, de propargyles, d’aryles, de benzyles et d’alcynyles conduisent à une grande variété de composés fluorés jamais décrits dans la littérature.Les méthodes de synthèse développées dans ce travail sont originales et permettent la synthèse d’une grande famille de composés fluorés avec un moindre coûtThe development of a simple method to obtain perfluoroalkylated building blocks for their subsequent utilization in the synthesis of Rf-containing compounds is therefore essential to organofluorine chemistry. Perfluoroalkylated vinyl metals constitute an important class of these building blocks.In order to prepare a new perfluoroalkylated bulding blocks, we investigated transition metal-catalyzed-free hydrostannylation of ethyl 4,4,4-trifluorobut-2-ynoate 1. The hydrostannylation took place smoothly in the absence of additive, providing regioselectively high yields of the corresponding α or β stannylated alkenoates depending on the nature of the solvent used. Indeed, we have demonstrated that the hydrostannylation of 1 in hexane provided the β-stannylated product with high regioselectivity (>95%) and excellent yield (>97%). Using methanol as solvent, total α-regioselectivity of the hydrostannylation of 1 was observed, providing α -tributylstannylacrylate as the sole regioisomer in a nearly quantitative yield.Theses new vinyltins reagents readily undergo copper (I) catalyst coupling reactions with various electrophiles as allyl, propargyl, benzyl and alkynyl bromides to provide good yields of the new corresponding acrylates esters bearing a β-trifluoromethyl group.This method provided a new efficient entry to this important class of compounds
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Huang, Shu-Ru, and 黃淑如. "Regioselectivity in Friedel-Crafts Acylation Reaction:3- Substituted Phthalic Anhydrides." Thesis, 1996. http://ndltd.ncl.edu.tw/handle/58048175611625547153.
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Elliott, Christine Elizabeth. "Exploiting the geminal acylation reaction to produce a gbs-turn peptidomimetic /." 2001.
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Chinn, Tonya S. L. "Regioselectivity in Diels-Alder reactions and probing the use of the geminal acylation reaction for the formation of a steroid /." 2005.
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Melanson, Rhea Lise. "Examination of the geminal acylation reaction and its application towards the synthesis of a steroid backbone /." 2000.
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Han, Yu-An, and 韓喻安. "Stereoselectivity in Synthesis of Fluorine-Containing Ethylene from Acylation and Addition-Elimination Reaction of Monofluorophosphnate." Thesis, 2015. http://ndltd.ncl.edu.tw/handle/33761930605151920436.
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碩士國防大學理工學院
化學工程碩士班
103
Deprotonation of (EtO)2P(O)CFHCO2Et with n-Butyl lithium at tetrahydrofuran solvent affords phosphonate carbanion [(EtO)2P(O)CFCO2Et]-Li+ intermediate. Based on this carbanion, two-step reaction to prepare a series of fluorine-containing tetrasubstituted ethylene (R1R2C=CFCO2Et) are studied in this research. Acylation of phosphonate carbanion with R1C(O)Cl achieves ((EtO)2P(O)CFC(O)R1CO2Et). Subsequently, nucleo-philic addition of Grignard reagent R2MgX to the acylated phosphonate via HWE reaction affords (E/Z)-stereoselectivity of R1R2C=CFCO2Et. Compare to the one-step reaction which directly reacts of (EtO)2P(O)CFHCO2Et with aldehyde and ketone, the advantage of two-step reaction can put the different function group at -carbon position. In the synthesis of 3-CF3(C6H4)(C6H5)C=CFCO2Et compound, 78 % E-isomer was observed. Meanwhile E-isomer which contain 52 %-66 % as the major product in the preparation of R1(C6H11)C=CFCO2Et. Addition HMPA in the synthesis of 3-CF3(C6H4)(C6H5)C=CFCO2Et gives 93 % of E-isomer. Furthermore, Z-isomer increases 41 % in the preparation of (2-CF3(C6H4)(C6H5)C= CFCO2Et) by adding DMPU cosolvent. No apparent effects are observed in the change of Z and E-isomer if the cosolvent is added after the acylation reagent or Grignard reagent during the reaction processin the synthesis of 4-CF3(C6H4)(C6H5)C= CFCO2Et compound.
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Chen, Po-Lin, and 陳柏霖. "Preparation and properties of lithium-ion battery additives by the acylation reaction using five-membered heterocyclic and trifluoroacetic anhydride." Thesis, 2014. http://ndltd.ncl.edu.tw/handle/r78t3n.
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碩士國立臺北科技大學
化學工程研究所
102
The purpose of this study is to synthesize four kinds of trifluoroacetyl ketones by the acylation reaction using four different aromatic five-membered heterocyclic rings and trifluoroacetic anhydride, their structures were identified by Frustrated Total Internal Reflection and Nuclear Magnetic Resonance spectrometer, the unacylated five-membered heterocyclic rings(0.03wt.%) and acylated products(0.03wt.% and 0.05wt.%) were added as an additive into the liquid electrolyte(1M LiPF6 in EC:DEC(1:1)), and assembled these into the coin cells, electrochemical properties were measured by charge-discharge tests. In the constant current discharge-charge test shows that the addition of 3% five-membered heterocyclic rings additive is able to increase battery cycle life and reducing decay rate at most to 2.01% from 3.11%. The increase of first cycle discharge capacity by 4-6 mAh/g, poor battery cycle life and larger decay rate are showed in the addition of 3% acylated products. Decrease of battery capacity and cycle life with addition of 5% acylated products additive.
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Pavlatová, Jana. "Aplikace analytických metod ke studiu heterogenních katalytických procesů." Master's thesis, 2010. http://www.nusl.cz/ntk/nusl-284896.
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Acylation of cyclohexene can provide number of reaction products. Cyclohexene, 1-methylcyclohexene and 3-methylcyclohexene were acylated with propionic anhydride over diferent zeolite structures and molecular sieves. Cyclohexene acylation led to propionylcyclohexene. The major acylation products of 1-methylcyclohexene is 2-methyl-3-propionylcyclohexene. Reaction product of 3-methylcyclohexene acylation is 4-methyl-3-propionylcyklohexene and 3-methyl-2-propionylcyclohexene. The aim of acylation biphenyl with carboxylic acid anhydrides and chlorides was to prove reaction with the highest conversion of substrate. The highest biphenyl conversion was obtained with octanoyl chloride and hexanoic anhydride over zeolite USY (15). The highest selectivity to 4-acylbiphenyl was observed.
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Yogesh, S. "Design and Development of Metal-free Cross Dehydrogenative Coupling Reactions for the Construction of C-S, C-O and C-C bonds." Thesis, 2017. http://etd.iisc.ernet.in/2005/3698.
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The thesis entitled “Design and Development of Metal-Free Cross Dehydrogenative Coupling Reactions for the construction of C-S, C-O and C-C bonds” is divided into three Chapters. Chapter 1 is presented in five parts, which reveals the cross dehydrogenative coupling (CDC) strategies for the C–S bond forming reactions through C–H functionalization strategy using heterocyclic thiols and thiones. Chapter 2 presents tetrabutyl ammonium iodide (TBAI) catalyzed chemoselective α-aminoxylation of ketones with N-hydroxyimidates using TBHP as oxidant under cross dehydrogenative coupling (CDC) strategy. Chapter 3 describes a transition metal-free Minisci reaction for the acylation of isoquinolines, quinolines, and quinoxaline.
Chapter 1
Iodine Promoted C-S Bond Forming Reactions using Dimethyl Sulfoxide as an Oxidant
Chapter 1 reveals the utility of cross dehydrogenative coupling (CDC) reactions for the formation of C–S bonds by employing C–H functionalization strategies.1 The direct functionalization of C–H bonds to form C–C and C–X (N, O, S and P) bonds using metal-free reaction conditions is an interesting research topic in recent years.2 Use of dimethyl sulfoxide as an oxidant is emerging as one of the research topics of great interest and utility.3 Heterocyclic thiols and thiones are important precursors for synthesizing a variety of pharmaceuticals and biologically active compounds.4 Therefore it is useful to develop CDC reactions using heterocyclic thiols and thiones as precursors. In this chapter, we describe CDC reactions of heterocyclic thiols and thiones for the sulfenylation of ketones, aldehydes, α, β unsaturated methyl ketone derivatives, pyrazolones, enaminones and imidazoheterocycles using DMSO as an oxidant
Chapter 1: Part 1
Iodine Promoted Regioselective α-Sulfenylation of Carbonyl Compounds using Dimethyl Sulfoxide as an Oxidant: In this chapter, a rare regioselective C–H sulfenylation of carbonyl compounds with heterocyclic thiones and thiols have been described using iodine and dimethyl sulfoxide as reagents. Thus, dimethyl sulfoxide (as an oxidant) and stoichiometric amount of iodine have been used for the sulfenylation of ketones using heterocyclic thiones. Whereas the sulfenylation of ketones with heterocyclic thiols required catalytic amount of iodine. This protocol offers a rare regioselective sulfenylation of (i) methyl ketones in the presence of more reactive α-CH2 or α-CH groups, and (ii) aldehydes under CDC method. A few representative examples are highlighted in Scheme 1.5 The application of this methodology has been demonstrated by synthesizing a few precursors for Julia-Kocienski olefination intermediates.
Scheme 1. Iodine promoted rare regioselective α-sulfenylation of ketones and aldehydes
Siddaraj , Y.; Prabhu, K. R. Org. Lett. 2016, 18, 6090
Chapter 1: Part 2
Regioselective Sulfenylation of α’-CH3 or α’-CH2 Groups of α, β Unsaturated Ketones using
Dimethyl Sulfoxide as an Oxidant: In this chapter, an interesting regioselective sulfenylation of α’-CH3 or α’-CH2 groups of α, β unsaturated ketones using dimethyl sulfoxide as an oxidant and catalytic amount of aq. HI (20 mol %) as an additive has been described. This eco-friendly method uses readily available, inexpensive I2 or HI and DMSO. This methodology exhibits a high regioselectivity without forming Michael addition product in the presence of strong acid such as aq. HI or iodine, which is difficult to achieve under cross dehydrogenative coupling (CDC) conditions. Current methodology exhibits a broad substrate scope. A few examples are shown in Scheme 2.6
Scheme 2. HI and DMSO promoted α’-sulfenylation of α, β unsaturated ketones
Siddaraju, Y.; Prabhu, K. R. (Manuscript submitted)
Chapter 1: Part 3
Iodine Catalyzed Sulfenylation of Pyrazolones using Dimethyl Sulfoxide as an Oxidant: In this chapter, a sustainable and efficient strategy for the sulfenylation of pyrazolones has been described using metal-free conditions by employing DMSO as an oxidant and iodine as a catalyst. A variety of heterocyclic thiols, heterocyclic thiones and disulfides undergo C–H functionalization reaction with pyrazolone derivatives furnishing the corresponding sulfenylated products in short time. Most of the products are isolated in pure form without column purification. A few examples are presented in Scheme 3.7
Scheme 3. Iodine promoted sulfenylation of pyrazolones
Siddaraju, Y.; Prabhu, K. R. Org. Biomol. Chem. 2017, 15, 5191
Chapter 1: Part 4
Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: Sulfenylation of Enaminones using Dimethyl Sulfoxide as an Oxidant: In this chapter, synthesis of poly functionalized aminothioalkenes has been described using substoichiometric amount of iodine and DMSO as an oxidant. This metal-free methodology enables a facile sulfenylation of enaminones with heterocyclic thiols and thiones. This methodology is one of the simple approaches for the sulfenylation of enaminones under cross dehydrogenative coupling method. A few examples are highlighted in Scheme 4.8
Scheme 4. Cross-dehydrogenative coupling approach for sulfenylation of enaminones
Siddaraju, Y.; Prabhu, K. R. J. Org. Chem. 2017, 82, 3084
Chapter 1: Part 5
Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles using DMSO as an Oxidant: In this chapter, a simple synthetic approach for the regioselective sulfenylation of imidazoheterocycles using iodine as a catalyst and DMSO as an oxidant under cross dehydrogenative coupling (CDC) reaction conditions has been demonstrated. This protocol provides an efficient, mild and inexpensive method for coupling heterocyclic thiols and heterocyclic thiones with imidazoheterocycles. This is the first report on sulfenylation of imidazoheterocycles with heterocyclic thiols and heterocyclic thiones under metal-free conditions. A few examples are shown in Scheme 5.9
Scheme 5. Cross-dehydrogenative coupling approach for sulfenylation of imidazoheterocycles
Siddaraju, Y.; Prabhu, K. R. J. Org. Chem. 2016, 81, 7838
Chapter 2
Chemoselective α-Aminoxylation of Aryl Ketones: Cross Dehydrogenative Coupling Reactions Catalyzed by Tetrabutyl Ammonium Iodide: In this chapter, chemoselective α-aminoxylation of ketones with N-hydroxyimidates catalyzed by tetrabutyl ammonium iodide (TBAI) has been presented. The coupling reaction of a variety of ketones with N-hydroxysuccinimide (NHSI), N-hydroxyphthalimide (NHPI), N-hydroxybenzotriazole (HOBt) or 1-hydroxy-7-azabenzotriazole (HOAt) using TBHP as oxidant has been investigated. This α-aminoxylation of ketones is chemoselective as aryl methyl ketones, aliphatic ketones as well as benzylic position are inactive under the reaction condition. A few examples are highlighted in Scheme 6.10 The application of this method has been demonstrated by transforming a few coupled products into synthetically useful vinyl phosphates.
Scheme 6. Chemoselective α-aminoxylation of ketones with N-hydroxyimidates
Siddaraju, Y.; Prabhu, K. R. Org. Biomol. Chem. 2015, 13, 11651
Chapter 3
A Transition Metal-Free Minisci Reaction: Acylation of Isoquinolines, Quinolines, and Quinoxaline: In this chapter, transition metal-free acylation of isoquinoline, quinoline and quinoxaline derivatives with aldehydes has been described by employing TBAB (tetrabutyl ammonium bromide, 30 mol %) and K2S2O8 as an oxidant under cross dehydrogenative coupling (CDC) reaction. This intermolecular acylation of electron-deficient heteroarenes provides an easy access and a novel acylation method of heterocyclic compounds. The application of this CDC strategy has been illustrated by synthesizing isoquinoline-derived natural products. A few representative examples are shown in Scheme 7.11
Scheme 7. CDC reactions of heteroarenes with aldehydes
Siddaraju, Y.; Lamani, M.; Prabhu, K. R. J. Org. Chem. 2014, 79, 3856
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Chang, Wei-Hsuan, and 張維軒. "(a)The New Saccharin Salts Used in the Catalytic Acylation Reaction and Recycling(b)High Efficient Bis(fluoro-ponytailed) Bipyridine Ruthenium complexes containing Tetrabutylammonium for Dye-Sensitized Solar Cells." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/76cz29.
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碩士國立臺北科技大學
有機高分子研究所
100
(a)The New Saccharin Salts Used in the Catalytic Acylation Reaction and Recycling We had successfully synthesized and purified the salt made of DMAP and saccharin. It’s surprising to discover that DMAP-salt and the other salts have the similar structure, and they can used in the catalytic esterification reaction of the alcohol. Conversion yield percentage and reaction time compared with the literature data, the overall efficiency of the reaction about 30 times. However, the reaction without adding solvents and bases can be carried out at room temperature. This discovery is based on the crystallization for series of saccharin and saccharin’s compounds. In the thesis, we improve the disadvantages of catalysts recycling. The non-polar solvents can soluble the acylation product, but catalyst can’t. We use catalyst insoluble characteristics through the centrifuge can easily recycle catalysts. Furthermore, the recycle-easy catalysts are based on concept of modern green technology. (b)High Efficient Bis(fluoro-ponytailed) Bipyridine Ruthenium complexes containing Tetrabutylammonium for Dye-Sensitized Solar Cells We used particular by designed bis(fluoro-ponytailed) bipyridine binding with rethenium. After purification of crude dye by column chromatography, the product was analyzed and spectroscopically characterized by multi-nuclei NMR (1H, 19F and 13C), FTIR and FAB. We synthesis of the CT series of dyes containing different tetrabutylammonium numbers had H1TBA3 and H3TBA1 two types. Dye molecules with different tetrabutylammonium numbers of photoelectric conversion efficiency. UV-vis, CV and other instruments measured results compared with the N719. We study the different tetrabutylammonium numbers of the dye in the optical, electrochemical and photoelectric conversion efficiency.
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Lee, Chia-Jui, and 李家睿. "Direct β-Acylation of 2-Arylidene-1,3-indandiones withAcyl Chlorides Catalyzed by OrganophosphanesPreparation of Furo[3,2-c]coumarins from 3-cinnamoyl-4-hydroxy-2H-chromen-2-ones and Acyl Chlorides: A Bu3P-Mediated C-Acylation/Cyclization SequenceSynthesis of Functionalized Furans via Chemoselective Reduction/Wittig reaction Using Catalytic Triethylamine and Phosphine." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/58559388773676205184.
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博士國立臺灣師範大學
化學系
104
In part I, we have developed an organophosphane-catalyzed direct β-acylation of a series of conjugated systems bearing ketone, amide and ester functionalities using acyl chlorides as trapping reagents. A wide variety of highly functional ketone derivatives were generated efficiently under very mild conditions with high yields according to our protocol. Our adducts can even be utilized as important building blocks for the synthesis of functional tri/tetracyclic pyridazine derivatives. In part II, electrophilic addition of acyl chlorides to 3- cinnamoyl-4-hydroxy -2H-chromen-2-ones and subsequent Bu3P-mediated cyclization leads to highly functionalized furo[3,2-c]coumarins. The unprecedented cyclization reaction proceeds under mild reaction conditions within short reaction times (1 min to 1 h), and can be further applied in the synthesis of alkenyl-substituted furo[3,2-c]coumarins by the treatment with carbonyl electrophiles under basic conditions. In part III, An efficient protocol for the synthesis of highly functionalized furans via intramolecular Wittig reaction has been developed using catalytic amounts of phosphine and triethylamine in the presence of silyl chloride, which served as the promoter to activate the phosphine oxide. Reduction of the activated phosphine oxide by hydrosilane resulted in the generation of phosphine, while the decomposition of conjugate acid of Et3N resulted in the regeneration of base, both of which mediated the formation of phosphorus ylide.
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Moulins, Jonathan. "Synthesis of Heterocycles via Chemoselective Geminal Acylation of 2-Methoxyoxazolidines, E/Z Isomerization in the Metathesis of Allyl Alcohol Derivatives with a First-Generation Ruthenium Catalyst, and Interception of Nazarov Reaction Intermediates of Allenyl Vinyl Ketones with Arenes." 2013. http://hdl.handle.net/10222/37454.
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Heterocycles were prepared through the geminal acylation of 2-methoxyoxazolidines with 1,2-bis(trimethylsilyloxy)cyclobutene. It was found that when water was excluded from the standard reaction conditions, regioselectivity of the ring expansion step was reversed, resulting in preferential rupturing of the endocyclic C-O bond instead of the C-N bond. Further cyclization resulted in the generation of 6,5-fused ring systems. The aqueous procedure was found to be applicable to 1,2-bis(trimethylsilyloxy)cyclopentene, resulting in the analogous 6,6-fused ring systems, while the anhydrous procedure failed to promote ring expansion. Tricyclic 6,5,6-fused ring systems were obtained with meso-7,8-bis(trimethylsilyloxy)bicyclo[4.2.0]oct-7-ene using the anhydrous procedure, while the intermediate generated under aqueous conditions failed to undergo ring closing. Allylic alcohol derivatives were subjected to homodimerization in the presence of a first-generation ruthenium catalyst. Previous work suggested that thermodynamic equilibration to the E-isomer was not a significant process for first-generation catalysts. However, product E/Z ratios were, in general, observed to increase significantly over time. In addition, an atmosphere of ethylene promoted reversion to the terminal olefins, leading to rapid E/Z equilibration, albeit at the expense of yield. Brief exposure to ethylene over the course of reaction resulted in a high E/Z ratio in a moderate yield. A 6,6,5-fused ring system was synthesized via the tandem Nazarov cyclization-intramolecular Friedel-Crafts alkylation of the corresponding allenyl vinyl ketone. The presence of electron donating substituents on the arene, as well as a two-carbon tether linking the arene to the allenyl vinyl ketone, were crucial to the success of the reaction. The intermolecular trapping of an allenyl vinyl ketone with substituted arenes was also investigated. Trapping occurred primarily at the electronically preferred position a, while sterically encumbered substrates tended to trap preferentially at the less hindered position c. Surprisingly, 1,3,5-trisubstituted arenes trapped almost exclusively at position a, having overcome significant steric crowding, demonstrated by hindered rotation about the newly formed carbon-carbon bond.
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ZUO, XI-HUA, and 左西華. "Direct alkylation, acylation and trimethylsilylation reactions of 3-sulfolenes and its applications on synthesis." Thesis, 1986. http://ndltd.ncl.edu.tw/handle/72142918027472132575.
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Larionov, Evgeny [Verfasser]. "Activity and selectivity of DMAP derivatives in acylation reactions : experimental and theoretical studies / von Evgeny Larionov." 2011. http://d-nb.info/1012856518/34.
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許家寧. "Direct β–Acylation of 2-Arylidine-1,3-Indandiones Catalyzed by Organophosphanes and Preparation of Indoles and Furans via Chemoselective Intramolecular Wittig Reactions." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/20040856161350271448.
Full textAbstract:
碩士國立臺灣師範大學
化學系
101
This thesis is divided into two parts: direct β–acylation of 2-Arylidine-1,3-indandiones catalyzed by organophosphanes (part I), and synthesis of indoles and furans via chemoselective intramolecular Wittig reactions (part II). In the first part, we have developed a new synthetic method for β–acylation of 2-Arylidine-1,3-indandiones. In the reaction only catalytic amount of organophosphane was required to provide acylated products in up to 98% yield. Starting from various substituted 2-arylidene-1,3-indandiones and acyl chlorides in the presence of Et3N. Further application using acylated products as starting materials was also performed to afford pyridazine compounds in good yields. Compounds having indole framework are important for pharmaceutical aspect. In the second part, a developed protocol in our laboratory was utilized to synthesize indole compounds. In order to investigate the chemoselectivity of intramolecular Wittig reactions, we designed ylides as reactive intermediates with both ester and amide functionalities.