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1

Hedfors, Cecilia. "Lipase chemoselectivity - kinetics and applications." Licentiate thesis, KTH, School of Biotechnology (BIO), 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-10232.

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A chemoselective catalyst is preferred in a chemical reaction where protecting groups otherwise are needed. The two lipases Candida antarctica lipase B and Rhizomucor miehei lipase showed large chemoselectivity ratios, defined as (kcat/KM)OH / (kcat/KM)SH, in a transacylation reaction with ethyl octanoate as acyl donor and hexanol or hexanethiol as acyl acceptor (paper I). The chemoselectivity ratio of the uncatalyzed reaction was 120 in favour of the alcohol. Compared to the uncatalyzed reaction, the chemoselectivity was 730 times higher for Candida antarctica lipase B and ten times higher for Rhizomucor miehei lipase. The KM towards the thiol was more than two orders of magnitude higher than the KM towards the corresponding alcohol. This was the dominating contribution to the high chemoselectivity displayed by the two lipases. In a novel approach, Candida antarctica lipase B was used as catalyst for enzymatic synthesis of thiol-functionalized polyesters in a one-pot reaction without using protecting groups (paper II). Poly(e-caprolactone) with a free thiol at one of the ends was synthesized in an enzymatic ring-opening polymerization initiated with mercaptoethanol or terminated with either 3-mercaptopropionic acid or g-thiobutyrolactone.

 

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2

Morey, James Vaughan. "Controlling the chemoselectivity of directed metallation." Thesis, University of Cambridge, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.612284.

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3

Malmgren, Joel. "Iodonium Salts : Preparation, Chemoselectivity and Metal-Catalyzed Applications." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-107694.

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This thesis concerns the preparation and use of diaryliodonium salts. In Project I various unsymmetrical diaryliodonium salts were reacted with three different nucleophiles in order to study the chemoselectivity of the reactions of the salts. The main focus of this project was to gain a deeper understanding of the underlying factors that affect the chemoselectivity in transition metal-free arylation reactions. They were found to be very nucleophile-dependent. Some nucleophiles were very sensitive to electronic effects, whereas others were sensitive to steric factors. Ultimately, some arenes are never transferred. A very interesting scrambling reaction was also observed under the reaction conditions, where unsymmetrical diaryliodonium salts form symmetrical salts in situ. Project II details the preparation of N-heteroaryliodonium salts via a one-pot procedure. The salts were designed so that the N-heteroaryl moiety was selectively transferred in applications both with and without transition metals. The chemoselectivity was demonstrated by selective transfer of the pyridyl group onto two different nucleophiles. The third project in the thesis discusses the synthesis of alkynyl(aryl)iodonium salts and alkynylbenziodoxolones from arylsilanes. This protocol could potentially be a very useful complement to the existing procedures, in which boronic acids are used. The last part of the thesis (Project IV) describes a C-2 selective arylation of indoles where diaryliodonium salts were used in combination with hetero-geneous palladium catalysis. This transformation was performed in water at ambient temperature to 50 °C, and tolerated variations of both the indole and the diaryliodonium salt. Importantly, several N-H indoles could be arylated. The MCF-supported Pd-catalyst showed very little leaching and it was demonstrated that the main part of the reaction occurred via heterogeneous catalysis.

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Accepted.

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4

Volkov, Alexey. "Catalytic Amide Reductions under Hydrosilylation Conditions." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-129028.

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This thesis covers the development of catalytic methodologies for the mild and chemoselective reductions of amides. The first part of the thesis describes the use of a Fe(II)/NHC catalyst for the deoxygenation of aromatic tertiary amides to corresponding amines. The protocol is characterized by low catalyst loading, mild reaction conditions and the use of air and moisture stable polymethylhydrosilaxane (PMHS) as the hydride source. The second part concerns the development of a protocol for the room temperature deoxygenation of a wide range of tertiary amides to amines using catalytic amounts of Et2Zn and LiCl together with PMHS. The system displayed high levels of chemoselectivity tolerating various reducible groups such as nitro, nitrile, and olefin functionalities, and was shown to be applicable for the reduction of aromatic, heteroaromatic and aliphatic tertiary amides. The attempts to expand the scope of the Fe-based protocol to accommodate benzylic tertiary amides led to the development of a transition metal-free catalytic system based on KOtBu for the formation of enamines. The final products constitute an important class of precursors for a wide range of valuable compounds in organic chemistry. Moreover, avoiding the use of transition metals in the protocol allowed the desired products to be obtained without the hazardous metal contaminants. The last chapter of the thesis describes the Mo(CO)6-catalyzed hydrosilylation of amides. The Mo-based catalyst was proven to mediate the deoxygenation of α,β-unsaturated tertiary and secondary amides to the corresponding allylamines without reduction of the olefinic bonds. Further development of the catalytic system revealed an unprecedented chemoselectivity in the hydrosilylation of aromatic and certain aliphatic tertiary amides in the presence of a variety of reducible groups along with aldehydes and imines that were tolerated for the first time. Moreover, it was possible to control the reaction outcome by variation of the reaction temperature to obtain either amines or aldehydes as the major products. The synthetic utility of the developed Mo(CO)6-catalyzed protocols was further demonstrated in the synthesis of the pharmaceuticals Naftifine and Donepezil.
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5

Kamikawa, Takashi. "Enantioselectivity and Chemoselectivity in Palladium-Catalyzed Grignard Cross-Coupling of Aryl Triflates." 京都大学 (Kyoto University), 1998. http://hdl.handle.net/2433/157165.

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本文データは平成22年度国立国会図書館の学位論文(博士)のデジタル化実施により作成された画像ファイルを基にpdf変換したものである
Kyoto University (京都大学)
0048
新制・論文博士
博士(理学)
乙第9788号
論理博第1334号
新制||理||1061(附属図書館)
UT51-98-G387
(主査)教授 林 民生, 教授 鈴木 仁美, 教授 大須賀 篤弘
学位規則第4条第2項該当
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6

Marth, Gabriella. "The synthesis of polyfunctional pyrroles and the investigation of the chemoselectivity of their reactions." Thesis, University of Sunderland, 2009. http://sure.sunderland.ac.uk/3694/.

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Polyfunctional pyrroles are interesting heterocyclic intermediates as they have a range of reactive centres and the chemoselectivity of their reactions under a range of conditions, is therefore, of much interest. Polyfunctionalised heterocycles are relatively difficult to prepare, but the reactions of these substituted pyrroles allow access to a wide variety of new substituted heterocyclic compounds via these intermediates. The aim of this project was to synthesise polyfunctional pyrroles in order to investigate their use in the preparation of libraries and compounds with known biological activity. The synthesis and initial investigation of the regioselectivity of polyfunctional pyrroles, such as 3,5-dichloro-1H-pyrrole-2,4-dicarboxaldehyde, has previously been described; this work investigated only nucleophilic substitutions. We have investigated the chemoselectivity of the reaction of these pyrroles with a range of reagents and a number of pyrrole derivatives were synthesised via selective functional group transformations. All new compounds were fully characterised by spectroscopic and elemental analysis. Another aim of this project was to discover novel agents that inhibit VEGF receptors using structure based drug design. We have identified hit compounds and synthesised them using regioselective reactions of functional groups present on the pyrrole ring. The compounds were tested for anti-proliferative activity against the HaCaT, human keratinocyte cell line, and also against HT29 and CaCo-2, human colon cell lines using the MTT assay.
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7

Sandford, Christopher. "The reactivity and chemoselectivity of nucleophilic boronate complexes : applications in cross-coupling, fluorination and trifluoromethylation." Thesis, University of Bristol, 2017. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.730846.

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8

Blanco, Jiménez Carolina. "Norbornene functionalization through asymmetric pd- and rh-catalyzed carbonylation processes." Doctoral thesis, Universitat Rovira i Virgili, 2010. http://hdl.handle.net/10803/9109.

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Esta tesis se ha centrado en el estudio de las reacciones de carbonilación de norborneno catalizada por metales. Este sustrato puede ser funcionalizado a través de este proceso, empleando sistemas catalíticos y condiciones de reacción adecuadas, en productos intermedios con aplicación en la industria de perfumes y química fina. En este trabajo se han llevado a cabo estudios en la reacción de metoxicarbonilación de norborneno catalizada por paladio empleando ligandos monofosfina y difosfina logrando un importante control de la selectividad hacia la formación del producto deseado. Algunos aspectos mecanísticos de esta reacción han sido desarrollados empleando métodos de resonancia magnética nuclear que incluyen experimentos de alta presión. Finalmente, se ha estudiado la reacción de hidroformilación asimétrica de norborneno catalizada por complejos de rodio usando ligandos difosfito derivados de carbohidrato. Estos sistemas catalíticos han mostrado alta actividad y selectividad con excesos enantioméricos moderados.
This thesis focuses on the study of the metal-catalyzed carbonylation of norbornene. The transformation of this substrate in esters and aldehydes offers potential applications for the production of valuable compounds in fine chemistry and perfumery industry. In this work we have performed studies on the palladium-catalyzed methoxycarbonylation of norbornene bearing monodentate and bidentate phosphine ligands achieving an important control of the selectivity towards the formation of the desired product. Mechanistic aspects of this reaction have been developed using nuclear magnetic resonance methods, including High-Pressure techniques. Finally, we have studied the asymmetric rhodium-catalyzed hydroformylation of norbornene using chiral 1,3-diphosphites ligands derived from carbohydrates. These catalytic systems have shown high activities with excellent stereoselectivities and moderate enantioselectivities.
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9

Rueda, Becerril Montserrat. "Fluorination of alkyl radicals using electrophilic N-F reagents and investigation on the intramolecular chemoselectivity of alkoxy radicals." Thesis, University of British Columbia, 2014. http://hdl.handle.net/2429/51510.

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The selective fluorination of organic molecules has become increasingly important for the pharmaceutical and agrochemical industries, given that the presence of this atom enhances the lipophilicity and bioavailability of molecules. Despite the extensive research in fluorine chemistry, there is a paucity of selective and safe sources of fluorine for radical reactions. I hereby present the investigation of N−F reagents as efficient fluorine atom transfer agents to alkyl radicals. Although most of the research presented in this work focuses on fluorination methodologies, a study on the intramolecular chemoselectivity of alkoxy radicals is also discussed. Chapter 2 describes the exploratory work into the feasibility of transferring a fluorine atom to alkyl radicals from electrophilic sources of fluorine. Diacyl peroxides and t-butylperesters were homolyzed to generate alkyl radicals in the presence of different N−F fluorine sources. Primary, secondary, and tertiary fluoroalkanes were successfully synthesized under the reaction conditions. This methodology was successfully applied to the fluorination of a cholic acid derivative. In Chapter 3, photoredox catalysis was explored as an alternative method to generate alkyl radicals in the context of radical fluorination. Trisbipyridylruthenium (II) and visible light were utilized to promote the decarboxylative fluorination of phenoxyacetic acid derivatives. Electronwithdrawing groups on the aryl ring favoured the transformation, while electron-donating groups provided undesired products. An estrone derivative was successfully fluorinated with our visible-light mediated methodology. Additionally, transient absorption spectroscopy studies in collaboration with the Wolf group at the University of British Columbia, along with cyclic voltammetry experiments performed in collaboration with the Bizzotto group at the same institution, provided evidence to support an oxidative mechanism of the photocatalytic cycle. Chapter 4 describes a study to assess the chemoselectivity of alkoxy radical cyclizations onto silyl enol ethers, when other radical pathways can occur. Cyclization of intramolecular competition substrates showed that 5-exo cyclization of alkoxy radicals onto silyl enol ethers were preferred over 5-exo cyclizations onto terminal, disubstituted and trisubstituted alkenes, as well as 1,5-hydrogen atom transfer reactions and β-fragmentations. Silyl enol ethers as alkoxy radical acceptors strongly favour 6-exo cyclization over 1,5-hydrogen atom transfer from an allylic position.
Science, Faculty of
Chemistry, Department of
Graduate
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10

Jalalian, Nazli. "Development and Applications of Hypervalent Iodine Compounds : Powerful Arylation and Oxidation Reagents." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-75810.

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The first part of this thesis describes the efficient synthesis of several hypervalent iodine(III) compounds. Electron-rich diaryliodonium salts have been synthesized in a one-pot procedure, employing mCPBA as the oxidant. Both symmetric and unsymmetric diaryliodonium tosylates can be isolated in high yields. An in situ anion exchange also enables the synthesis of previously unobtainable diaryliodonium triflates. A large-scale protocol for the synthesis of a derivative of Koser’s reagent, that is an isolable intermediate in the diaryliodonium tosylate synthesis, is furthermore described. The large-scale synthesis is performed in neat TFE, which can be recovered and recycled. This is very desirable from an environmental point of view. One of the few described syntheses of enantiopure diaryliodonium salts is discussed. Three different enantiopure diaryliodonium salts bearing electron-rich substituents are synthesized in moderate to high yields. The synthesis of these three salts shows the challenge in the preparation of electron-rich substituted unsymmetric salts. The second part of the thesis describes the application of both symmetric and unsymmetric diaryliodonium salts in organic synthesis. A metal-free efficient and fast method for the synthesis of diaryl ethers from diaryliodonium salts has been developed. The substrate scope is wide as both the phenol and the diaryliodonium salt can be varied. Products such as halogenated ethers, ortho-substituted ethers and bulky ethers, that are difficult to obtain with metal-catalyzed procedures, are readily prepared. The mild protocol allows arylation of racemization-prone a-amino acid derivatives without loss of enantiomeric excess. A chemoselectivity investigation was conducted, in which unsymmetric diaryliodonium salts were employed in the arylation of three different nucleophiles in order to understand the different factors that influence which aryl moiety that is transferred to the nucleophile.

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Accepted. Paper 5: Submitted. Paper 6: Manuscript.

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11

Islam, Saidul. "Studies towards the chemical origins of life." Thesis, University of Manchester, 2011. https://www.research.manchester.ac.uk/portal/en/theses/studies-towards-the-chemical-origins-of-life(afeac977-39db-4caa-bcbc-63643f5e9f3e).html.

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The 'RNA World' hypothesis states that RNA was the first living system on the primitive Earth, where it carried out dual genotypic and phenotypic functions. Therefore, RNA must have self-assembled by purely chemical means from small prebiotic feedstock molecules. A plausible demonstration of the synthesis of RNA with the natural [5'→3'] phosphodiester linkage, and its self-replication has not been achieved so far. Some have speculated a 'simpler' informational polymer preceded it, and biology based on this polymer subsequently 'invented' RNA. The structurally simpler L-α-threofuranosyl nucleic acid (TNA) has been proposed as a primordial ancestor to RNA. A study into the potential self-assembly of TNA nucleotides was carried out. It is shown that as a direct result of TNA's structural simplicity, its generational chemistry is more difficult than RNA. The tetrose aminooxazolines are unstable under the conditions of its formation. The tetrose anhydronucleosides efficiently incorporate phosphate to form activated tetrose cytidine-2',3'-cyclic phosphates, but with the wrong stereochemistry. Strong support for the 'RNA world' hypothesis came from a report in 2009 of the prebiotic synthesis of activated pyridimine ribonucleoside-2',3'-cyclic phosphates. Oligomerisation studies were carried out on these activated monomers with various catalysts, and NMR studies were carried out to determine the aspects of their reactivity. It was found that only short oligomers are formed. However, nucleoside-2',3'-cyclic phosphates were found to selectively hydrolyse to a 2:1 mixture of 3' and 2'-monophosphates, and this observation was considered as etiologically relevant. Nucleoside-2' and 3'-monophosphates cyclise back to nucleoside-2',3'-cyclic phosphates upon phosphate activation, and so cannot be considered as direct candidates for oligomerisation. A chemistry that selectively uses the nucleoside-3'-phosphate for the synthesis of RNA, and recycles the unwanted 2'-phosphate would be highly desirable. Thus, a regio- and chemoselective reaction that selectively acetylates monomer and oligomer nucleoside-3'-phosphates at the 2'-hydroxyl in water is presented. Nucleoside-2'-phosphates are shown to acetylate less efficiently, and show a greater propensity to recyclise back to nucleoside-2',3'-cyclic phosphates. Purine nucleotides were also found to acetylate better than pyrimidines. This potentially primordial protecting group chemistry approach towards the prebiotic synthesis of RNA is conceptually novel, and has the potential to give a natural [5'→3'] phosphodiester linkage isomer. It is considered as a major step towards solving the long-standing problem of non-enzymatic self-replication of RNA.
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12

Brondani, Patrícia Bulegon. "Investigação da seletividade de mono-oxigenases frente a substratos orgânicos de boro ou de selênio." Universidade de São Paulo, 2012. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-03092012-142803/.

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Neste trabalho foi avaliada a seletividade (quimio ou enantiosseletividade) de quatro enzimas Baeyer-Villiger mono-oxigenases (BVMOs: PAMO, PAMO M446G, HAPMO e CHMO) frente a substratos contendo boro ou selênio. Inicialmente uma série de boro-acetofenonas foram submetidas à bio-oxidação catalisada por estas BVMOs. A enzima CHMO mostrou quimiosseletividade para transformação da ligação C-B em detrimento da reação de Baeyer-Villiger. Enquanto PAMO e PAMO M446G catalisaram a oxidação de ambas as funções em substratos 4-substituídos e a seletiva transformação de C-B no caso de substratos 3-substituídos. A enzima HAPMO levou a reação de Baeyer-Villiger e a transformação da ligação C-B em todos os casos. Quando alquenos contendo boro foram utilizados como substratos, somente aqueles que continham uma porção fenila em sua estrutura foram oxidados por BVMOs. Em nenhum dos casos foi observada reação de epoxidação e todas as enzimas levaram a transformação da ligação C-B em C-O. Compostos quirais contendo boro foram submetidos a reações com as BVMOs na tentativa de transformação enantiosseletiva. PAMO e PAMO M446G foram as melhores enzimas levando, na maioria dos casos, a satisfatória oxidação dos substratos. Entretanto, somente um composto pôde ser oxidado com boa enantiosseletividade (e.e 82-91%). Compostos quirais contendo o átomo de selênio também foram alvos de estudo com BVMOs. Novamente a enzima PAMO se mostrou a melhor opção dentre as enzimas testadas e somente quando R2 e R1 = Ph houve boa enantiosseletividade na oxidação (e.e 97 %).
In this work we evaluated the selectivity (chemo or enantioselectivity) of four Baeyer-Villiger mono-oxigenases (BVMOS: PAMO, M446G PAMO, HAPMO and CHMO) in the presence of boron-containing or selenium-containing compounds. Initially, a series of boron-acetophenones were submitted to oxidation reactions mediated by BVMOs. The enzyme CHMO was chemoselective leading only to C-B bond transformation instead Baeyer-Villiger reaction. However, PAMO and PAMO M446G mediated both oxidations in 4-substituted substrates, and only the C-B transformation in 3-substituted substrates. The enzyme HAPMO leading to Baeyer- Villiger reaction and C-B transformation in all cases. When boron-containing alkenes were the substrates, only compounds with phenyl moiety in the structure were oxidized by BVMOs. It was observed only the C-B transformation and none of the epoxidation reaction. Chiral boron compounds were submitted to BVMOS mediated reactions in an attempt of enantioselective transformation. PAMO and M446G PAMO showed the best results leading, in most cases, to a satisfactory oxidation. However, only one compound was oxidized with great enantioselectivity (82-91% ee). Selenium-containing chiral compounds were also tested in reactions mediated by BVMOs. Again, PAMO showed the best results among BVMOs tested, but only when R2 e R1 = Ph the reaction occurred with great enantiosselectivity (97 % ee).
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13

Fiss, Gabriela Fehn. "Síntese de heterociclos via reações de ciclocondensação de a-etiloxalil e -pirazolil(alquil) b-dimetilaminoenonas com1,2- OU 1,3-Dinucleófilos." Universidade Federal de Santa Maria, 2009. http://repositorio.ufsm.br/handle/1/4175.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico
Chemoselective synthesis of ethyl 4-pirimidinecarboxylates and/or ethyl 5-pirimidineoxalates via cyclocondensation reaction of b-dimethylaminoenones [R1C(=O)C(=CNMe2)C(=O)CO2Et, where R1 = Ph, 4-MeC6H4, 4-MeOC6H4, 4-BrC6H4, 4-ClC6H4, 4-FC6H4, 4-O2NC6H4, 2-thienyl, benzo[b]furan-2-yl and CF3] with NCN 1,3- dinucleophiles such as benzamidine hydrochloride or 1H-1-pyrazolyl-carboxamidine hydrochloride (50-86%); utilization of ethyl 4-pirimidinecarboxylates (when R1 = Ph, 4-MeOC6H4, 4-FC6H4 and 2-thienyl) in the cyclization reaction with hydrazine monohydrate, leading to 7,8-dihydropyrimido[4,5-d]pyridazin-8-ones (81-92%). In this work it was also studied the condensation reaction of (3,5-dimethyl-1H-1- pyrazolyl)alkylketones with N,N-dimethylformamide dimethylacetal, with the aim to obtain b-dimethylaminoenones [PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolyl), PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolylmethyl) and MeC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolyl)] (92-98%); and synthesis of 1,4 -biazoles via cyclocondensation reaction of b-dimethylaminoenones with different 1,2-dinucleophiles such as hydrazine monohydrate, terc-butylhydrazine hydrochloride,phenylhydrazine hydrochloride, carboxymethylhydrazine or hydroxylamine hydrochloride (50-80%). The X-ray diffraction technique was used in the elucidation of the stereochemistry of PhC(=O)C(=CNMe2)(3,5-dimethyl-1H-1-pyrazolylmethyl) and regiochemistry of the cyclocondensation reactions.
Síntese quimiosseletiva de 4-pirimidinocarboxilatos de etila e/ou 5-pirimidinoxalatos de etila via reação de ciclocondensação de b-dimetilaminoenonas [R1C(=O)C(=CNMe2)C(=O)CO2Et, onde R1 = Ph, 4-MeC6H4, 4-MeOC6H4, 4-BrC6H4, 4-ClC6H4, 4-FC6H4, 4-O2NC6H4, 2-tienil, benzo[b]furan-2-il e CF3] com 1,3-dinucleófilos do tipo NCN, tais como cloridrato de benzamidina ou cloridrato de 1H-1-pirazolil-carboxamidina (50-86%); utilização de 4-pirimidinocarboxilatos de etila (quando R1 = Ph, 4-MeOC6H4, 4-FC6H4 e 2-tienil) na reação de ciclização com monoidrato de hidrazina, levando a 7,8-diidropirimido[4,5-d]piridazin-8-onas (81- 92%). Neste trabalho, também foi estudada a reação de condensação de (3,5-dimetil-1H-1-pirazolil)alquilcetonas com N,N-dimetilformamida dimetilacetal, visando a obtenção de b-dimetilaminoenonas [PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolil), PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolilmetil) e MeC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolil)] (92-98%); e síntese de 1,4 -biazóis via reação de ciclocondensação de b-dimetilaminoenonas com diferentes 1,2-dinucleófilos, tais como monoidrato de hidrazina, cloridrato de terc-butilidrazina, cloridrato de fenilidrazina, carboximetilidrazina ou cloridrato de hidroxilamina (50- 80%). A técnica de difração de raios-X foi utilizada na elucidação da estereoquímica de PhC(=O)C(=CNMe2)(3,5-dimetil-1H-1-pirazolilmetil) e regioquímica das reações de ciclocondensação.
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14

Komiotis, Dimitri. "Synthese chimique et etude de substances cytotoxiques dirigees specifiquement contre les cellules cancereuses : conjugaison avec des proteines specifiques." Paris 7, 1988. http://www.theses.fr/1988PA077190.

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Synthese d'antitumoreux nucleosidiques et aminonucleosidiques et leur couplage avec des acides gras et des proteines a ete etudie. Mise au point d'une nouvelle methode de detritylation chimioselective
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15

Hammoud, Jana. "Evaluation des complexes dirhodium (II) tétraacétate-Carbène-N-Hétérocyclique pour la décomposition de diazoesters et applications en glycochimie Functionalization of GlucoPyranosides at position 5 by 1,5 C–H insertion of Rh(II)-Carbenes: Dramatic influence of the anomeric configuration." Thesis, Normandie, 2020. http://www.theses.fr/2020NORMIR03.

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Ces travaux de thèse ont concerné l’étude des propriétés catalytiques des complexes Rh₂L₄.NHC vis-à-vis des diazo esters, et leur application dans le domaine de la glycochimie. Nous avons tout d’abord développé une procédure expérimentale reproductible pour la préparation de ces complexes organométalliques. Par ailleurs, nous avons montré que le complexe Rh₂(OAc)₄.IMes était capable de décomposer de manière chimiosélective différentes familles de diazo esters, ouvrant ainsi la possibilité de la conception d’un système catalytique commutable. Dans le domaine de la glycochimie, les complexes Rh₂L₄.NHC ont permis d’amélioré les conditions expérimentales de la réaction de quaternarisation de la position anomèrique par fonctionnalisation de sa liaison C-H. Enfin, la quaternarisation de la position 5 de pyranosides par insertion 1,5 C-H d’un métallo-carbène de Rh(II) ancré sur la position primaire a été développée
This work deals with the study of the catalytic properties of Rh₂L₄.NHC complexes towards diazoesters, and their application in the field of glycochemistry. We first developed a reproducible synthetic procedure for the preparation of these organometallic complexes. Furthermore, we have shown that the Rh₂(OAC)₄.IMes complexe was inducing the chemoselective decomposition of diazo esters, depending on their electronic properties. This unprecedented property opened the way to a switchable catalytic system. In the field of glycochemistry, the Rh₂L₄.NHC complexes made possible to improve the experimental conditions for the quaternization reaction of the anomeric position by C-H bond functionalization. Finally, the quaternization of position 5 of pyranosides by 1,5 C-H insertion of a Rh (II) metallo-carbene anchored on the primary position was developed
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16

Nishimura, Rodolfo Hideki Vicente. "Preparação de novos carbenoides de magnésio visando à síntese de inibidores de protease do VIH-1." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/59/59138/tde-13052015-154647/.

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Carbenoides são intermediários altamente reativos que desempenham um papel fundamental em estratégias sintéticas modernas. Essas espécies são muito semelhantes aos carbenos no estado singleto, visto que possuem um caráter ambifílico e reagem por um mecanismo concertado, levando a produtos estereoespecíficos. Estudos preliminares demonstraram a versatilidade de um carbenoide misto de magnésio e lítio (ClCH2 MgCl·LiCl) na reação com diversos aldeídos aromáticos, alifáticos e heterocíclicos. Desta maneira, o objetivo deste trabalho foi estudar a quimiosseletividade de tal reagente e investigar a aplicação deste na síntese diasterosseletiva do (2S,3S)-N-Boc-3amino-1,2-epóxi-4-fenilbutano e seu diastereoisômero de configuração (2R,3S). Para a primeira parte do trabalho, selecionamos alguns aldeídos contendo grupos funcionais, tais como, ésteres, nitrilas, cetonas, amida, entre outros. De maneira geral, o carbenoide de magnésio mostrou-se muito eficiente e quimiosseletivo, levando a 14 cloridrinas funcionalizadas em bons rendimentos isolados, contudo, quando grupos doadores de elétrons estavam presentes na posição 4 do anel, o aldeído apresentou uma diminuição de reatividade e impossibilitou a obtenção do produto desejado. Por fim, estudos preliminares visando à preparação dos epóxidos de configuração (2S,3S) e (2R,3S) foram também realizados e os resultados são discutidos de forma detalhada no texto.
Carbenoids are a class of highly reactive intermediate compounds that play a key role in modern synthetic strategies. These species show a state very similar to that of singlet state carbenes since they have an ambiphilic character and react by a concerted mechanism, something that allows them to afford stereospecific products. Previous studies demonstrated the versatility of a mixed magnesium and lithium carbenoid (ClCH 2 MgCl·LiCl) in the reaction with a number of aromatic, aliphatic and heterocyclic aldehydes. In this way, the objective of this work was to study the chemoselectivity of such reagent and investigate its application in the diastereoselective synthesis of (2S,3S)-N-Boc-3-amino-1,2-epoxy-4-phenylbutane and its diastereoisomer of configuration (2R,3S). For the first part of the work we selected some aldehyde containing functional groups such as esters, nitriles, ketones and amide, among others. In summary, the magnesium carbenoid proved to be very efficient and chemoselective, leading to 14 functionalized chlorohydrins in good isolated yields. Nevertheless, when electron donating groups were present at the position 4 of the substrates ring, the resulting aldehyde showed a decrease in reactivity, which precluded us to obtain the desired product. Finally, preliminary studies aiming the preparation of the epoxides of configuration (2S,3S) and (2R,3S) were also investigated and the results are discussed in detail in the text.
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17

HOUTTEVILLE, MARIE-CLAIRE. "Etude de la simple et de la double diastereoselectivite de la reaction d'aldolisation de l'acide propanedithioique : synthese de beta-oxodithioesters par oxydation chimioselective de beta-hydroxydithioesters." Caen, 1988. http://www.theses.fr/1988CAEN2006.

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18

Millan, Cabrera Reisel. "Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory." Doctoral thesis, Universitat Politècnica de València, 2021. http://hdl.handle.net/10251/161934.

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[ES] En este trabajo estudiamos dos reacciones catalíticas relevantes para la industria y la localización del anión fluoruro en la zeolita RTH, sintetizada en medio fluoruro. El capítulo 3 es el primer capítulo de resultados, donde se estudia la reducción quimioselectiva del nitroestireno en las superficies Ni(111), Co(111), Cu(111) y Pd(111). El mecanismo generalmente aceptado de esta reacción está basado en el esquema propuesto por Haber en 1898, en el que la reacción puede transcurrir por dos rutas, la directa y la de condensación. En este capítulo exploramos ambas rutas, y observamos que la ruptura de los enlaces N-O y la consecuente formación de enlaces metal-O está más favorecida que la formación de enlaces N-H en las superficies Ni(111) y Co(111), debido al carácter oxofílico de ambos metales. Las etapas más lentas involucran la formación de enlaces N-H. En las superficies de metales nobles como Pt(111) y Pd(111) se observa el comportamiento contrario. La superficie Cu(111) es un caso intermedio comparado con los metales nobles y no nobles. Además, el nitroestireno interactúa con los átomos de Cu de la superficie solo a través de grupo nitro, con lo cual es un candidato ideal para alcanzar selectividades cerca del 100%. Sin embargo, la superficie Cu(111) no es capaz de activar la molécula de H2. En este sentido, proponemos un catalizador bimetálico basado en Cu, dopado con otro metal capaz de activar al H2, tales como el Pd o el Ni. En los capítulos 4 y 5 se ha estudiado la reducción catalítica selectiva de los óxidos de nitrógeno (SCR, en inglés) con amoníaco. Usando métodos de DFT, hemos encontrado rutas para la oxidación de NO a NO2, nitritos y nitratos con energías de activación relativamente bajas. También, hemos encontrado que la reducción de Cu2+ a Cu+ requiere la participación simultánea de NO y NH3. Posteriormente, hemos estudiado la influencia del NH3 en este sistema con métodos de dinámica molecular. El NH3 interacciona fuertemente con el Cu+ de forma que dos moléculas de este gas son suficientes para romper la coordinación del catión Cu+ con los oxígenos del anillo 6r, y formar el complejo lineal [Cu(NH3)2]+. Además, los cationes Cu2+ pueden ser estabilizados fuera de la red mediante la formación del complejo tetraamincobre(II). Debido a la presencia de los cationes Cu+ y Cu2+ coordinados a la red de la zeolita, aparecen bandas en la región entre 800-1000 cm-1 del espectro infrarrojo. El análisis de las frecuencias IR de varios modelos con Cu+ y Cu2+ coordinados al anillo 6r, o formando complejos con amoniaco indica que cuando los cationes Cu+ y Cu2+ están coordinados a los oxígenos del anillo 6r aparecen vibraciones entre 830 y 960 cm-1. Frecuencias en esta zona también se obtienen en los casos en que NO, NO2, O2 y combinaciones de dos de ellos están adsorbidos en Cu+ y Cu2+. Sin embargo, cuando los cationes Cu+ y Cu2+ están fuera del anillo (no hay enlaces entre los cationes de cobre y los oxígenos del anillo 6r) no se obtienen vibraciones de IR en esta región del espectro. Estos resultados indican que con el seguimiento del espectro IR durante la reacción SCR es posible determinar si los cationes Cu+ y Cu2+ están coordinados o no al anillo de 6r en las etapas de oxidación y reducción. Por último, hemos simulado el desplazamiento químico de 19F, δiso,, en la zeolita sintetizada RTH. El análisis del δiso de los distintos modelos utilizados nos ha permitido reconocer la simetría del material sintetizado, el cual pertenece al grupo espacial P1 y la nueva celda unidad ha sido confirmada experimentalmente por difracción de rayos X. Finalmente, hemos asignado la señal experimental que aparece en el espectro de 19F a -67.2_ppm, al F- localizado en un sitio T2, el cual es a su vez la posición más estable. Además, la señal a -71.8 ppm se ha asignado al anión F- localizado en un sitio T4.
[CA] En aquest treball estudiem dues reaccions catalítiques rellevants per a la indústria i la localització de l'anió fluorur en la zeolita RTH, sintetitzada al mig fluorur. El capítol 3 és el primer capítol de resultats, on s'estudia la reducció quimioselectiva del nitroestireno en les superfícies Ni(111), Co(111), Cu(111) i Pd(111). El mecanisme generalment acceptat d'aquesta reacció està basat en l'esquema proposat per Haver-hi en 1898, en el qual la reacció pot transcórrer per dues rutes, la directa i la de condensació. En aquest capítol explorem totes dues rutes, i observem que la ruptura dels enllaços N-O i la conseqüent formació d'enllaços metall-O està més afavorida que la formació d'enllaços N-H en les superfícies Ni(111) i Co(111), a causa del caràcter oxofílico de tots dos metalls. Les etapes més lentes involucren la formació d'enllaços N-H. En les superfícies de metalls nobles com Pt(111) i Pd(111) s'observa el comportament contrari. La superfície Cu(111) és un cas intermedi comparat amb els metalls nobles i no nobles. A més, el nitroestireno interactua amb els àtoms de Cu de la superfície sol a través de grup nitre, amb la qual cosa és un candidat ideal per a aconseguir selectivitats prop del 100%. No obstant això, la superfície Cu(111) no és capaç d'activar la molècula d'H2. En aquest sentit, proposem un catalitzador bimetàl·lic basat en Cu, dopat amb un altre metall capaç d'activar a l'H2, com ara el Pd o el Ni. En els capítols 4 i 5 hem estudiat la reducció catalítica selectiva dels òxids de nitrogen (SCR, en anglés) amb amoníac. Usant mètodes de DFT, hem trobat rutes per a l'oxidació de NO a NO2, nitrits i nitrats amb energies d'activació relativament baixes. També, hem trobat que la reducció de Cu2+ a Cu+ requereix la participació simultània de NO i NH3. Posteriorment, hem estudiat la influència del NH3 en aquest sistema amb mètodes de dinàmica molecular. El NH3 interacciona fortament amb el Cu+ de manera que dues molècules d'aquest gas són suficients per a trencar la coordinació del catió Cu+ amb els oxígens de l'anell 6r, i formar el complex lineal [Cu(NH3)2]+. A més, els cations Cu2+ poden ser estabilitzats fora de la xarxa mitjançant la formació del complex tetraamincobre(II). A causa de la presència dels cations Cu+ i Cu2+ coordinats a la xarxa de la zeolita, apareixen bandes a la regió entre 800-1000 cm-1 de l'espectre infraroig. L'anàlisi de les freqüències IR de diversos models amb Cu+ i Cu2+ coordinats a l'anell 6r, o formant complexos amb amoníac indica que quan els cations Cu+ i Cu2+ estan coordinats als oxígens de l'anell 6r apareixen vibracions entre 830 i 960 cm-1. Freqüències en aquesta zona també s'obtenen en els casos en què NO, NO2, O2 i combinacions de dues d'ells estan adsorbidos en Cu+ i Cu2+. No obstant això, quan els cations Cu+ i Cu2+ estan fora de l'anell (no hi ha enllaços entre els cations de coure i els oxígens de l'anell 6r) no s'obtenen vibracions d'IR en aquesta regió de l'espectre. Aquests resultats indiquen que amb el seguiment de l'espectre IR durant la reacció SCR és possible determinar si els cations Cu+ i Cu2+ estan coordinats o no a l'anell de 6r en les etapes d'oxidació i reducció. Finalment, hem simulat el desplaçament químic de 19F, δiso, en la zeolita sintetitzada RTH. L'anàlisi del δiso dels diferents models utilitzats ens ha permés reconéixer la simetria del material sintetitzat, el qual pertany al grup espacial P1 i la nova cel·la unitat ha sigut confirmada experimentalment per difracció de raigs X. Finalment, hem assignat el senyal experimental que apareix en l'espectre de 19F a -67.2 ppm, al F- localitzat en un lloc T2, el qual és al seu torn la posició més estable. A més, el senyal a -71.8 ppm s'ha assignat a l'anió F- localitzat en un lloc T4.
[EN] In this work, we have studied two heterogeneous catalytic reactions and the localization of the fluoride anion in the as-made RTH framework, synthesized in fluoride medium. The first results, included in chapter 3, correspond to the chemoselective reduction of nitrostyrene on different metal surfaces, i.e, Ni(111), Co(111), Cu(111) and Pd(111). Until very recently, the reduction of the nitro group was explained on the basis of the general mechanism proposed by Haber in 1898 where the reaction can follow two routes, the direct and condensation route. We have explored the relevant elementary steps of both routes and found that because of the oxophilic nature of Ni and Co, the steps involving the dissociation of N-O bonds and formation of metal-O bonds are significantly favored compared with the other steps on both metal surfaces. In addition, the most demanding steps in terms of energy involve the formation of N-H bonds. These findings are in contrast to those of noble metals such as Pt and Pd, where the opposite behavior is observed. The behavior of Cu(111) lies in between the aforementioned cases, and also no chemical bonds between the carbon atoms of the aromatic ring of nitrostyrene and the Cu(111) surface is formed. For this reason, it might be an ideal candidate to achieve nearly 100 % selectivity. However, the Cu(111) surface does not seem to activate the H2 molecule. In this regard, we propose a bimetallic Cu-based catalyst whose surface is doped with atoms of a H2-activating metal, such as Ni or Pd. On another matter, we have also investigated the selective catalytic reduction of nitrogen oxides (SCR-NOx) and the main results are presented in the following two chapters, 4 and 5. By using static DFT methods, we found pathways for the oxidation of NO to NO2, nitrites and nitrates with relatively low activation energies. We also found, in agreement with experimental reports, that the reduction of Cu2+ to Cu+ requires the simultaneous participation of NO and NH3. Later, molecular dynamics simulations allowed us to assess the influence of NH3. The strong interaction of NH3 with the Cu+ cation is evidenced by its ability to detach Cu+ from the zeolite framework and form the mobile linear complex [Cu(NH3)2]+. Cu+ is no longer coordinated to the zeolite framework in the presence of two NH3 molecules. This observation and the fact that the T-O-T vibrations of the framework produce bands in the 800-1000 cm-1 region of the IR spectrum when perturbed by the coordination of Cu+ and Cu2+ cations, indicate that bands in the 800-1000 cm-1 regions should be observed when both copper cations are bonded to the framework oxygens. Finally, we have also studied NMR properties of the as-made pure silica RTH framework, aiming at locating the compensating fluoride anion. The calculation of the 19F chemical shift in different T sites and comparison with the experimental NMR spectra shows that the as-made RTH belongs to the P-1 space group with 16 Si, 32 O atoms, one fluoride anion and one OSDA cation. These results have been confirmed experimentally by XRD. In addition, we have assigned the experimental signal of 19F at -67.2 ppm to the fluoride anion in a T2 site, which in turn is the most stable location found, and the signal of -71.8 ppm to a fluoride anion sitting in a T4 site.
My acknowledgements to “La Caixa foundation” for the financial support through “La Caixa−Severo Ochoa” International PhD Fellowships (call 2015), to the Spanish Supercomputing Network (RES), to the Centre de Càlcul de la Universitat de València, to the Flemish Supercomputer Center (VSC) of Ghent University for the computational resources and technical support, and to the Spanish Government through the MAT2017-82288-C2-1-P programme
Millan Cabrera, R. (2021). Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/161934
TESIS
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19

Leroy, Corinne. "Modèles du NADH en série pyrrolo(2,3-b)pyridine. Réduction d'une nouvelle gamme de substrats : les énamides. Rôle respectif des deux auxiliaires chiraux lors de réductions asymétriques." Rouen, 1994. http://www.theses.fr/1994ROUES031.

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Nous avons réduit, pour la première fois, avec un modèle du NADH en série pyrrolo 2,3-b pyridine, des énamides. Nous nous sommes notamment intéressés à la réduction de précurseurs de tétrahydroisoquinoléines et d'acides aminés. C'est ainsi que nous avons préparé la salsolidine avec un excès énantiomérique de 87% et un rendement de 90%. Nous avons également étudié le mécanisme de réduction des énamides par un modèle du NADH, ce qui nous a permis d'en délimiter le domaine de réduction. Enfin nous avons préparé de nouveaux modèles chiraux du NADH en série pyrrolo 2,3-b pyridine et nous avons étudié leur comportement en synthèse asymétrique. Nous avons alors mis en évidence l'influence exercée par un substituant chiral, extérieur à la structure 1,4-dihydropyridine, sur la réduction asymétrique d'un substrat. De plus, nous avons obtenu un modèle possédant une réactivité exceptionnelle
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20

Ratajczak, Fabien. "Synthèse et réactivité de nitroxydes chiraux." Université Joseph Fourier (Grenoble), 1997. http://www.theses.fr/1997GRE10134.

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Les nitroxydes sont des radicaux libres qui sont reduits en hydroxylamine ou oxydes en sel d'oxoammonium par des processus monoelectroniques reversibles. Les sels d'oxoammonium formes in situ oxydent notamment les alcools primaires et secondaires dans des conditions douces, catalytiques, et sont chimio et regioselectifs. Pour tester leurs potentialites en synthese asymetriques, deux methodes de synthese de nitroxydes chiraux a axe de symetrie c#2 ont ete mises au point. La premiere methode, originale, met en jeu la formation de dienolates en ,' d'aminodiesters suivie de leur reaction avec des electrophiles. Le dedoublement des amines d,l obtenues suivie d'une oxydation mene aux nitroxydes chiraux cycliques (cinq et six chainons) enantiomeriquement enrichis. La seconde strategie comporte deux additions nucleophiles successives sur des nitrones. Les nitroxydes optiquement actifs sont obtenus via un dedoublement d'amines. Une version enantioselective de cette methode a ete developpee a partir de la nitrone issue de la (2r,5r)-dimethylpyrrolidine. La stabilite des sels d'oxoammonium resultant de l'oxydation des nitroxydes prepares a ete etudiee par electrochimie. Ils sont peu stables, mais formes in situ ils catalysent l'oxydation des alcools. Certains d'entre eux sont capables de reconnaissance chirale dans le cas du dedoublement cinetique d'un alcool racemique ou de l'oxydation asymetrique d'un diol meso. Les exces enantiomeriques sont actuellement modestes, mais quelques resultats sont prometteurs. Enfin le nouveau systeme d'oxydation d'alcools primaires par le couple ncs/tempo mis au point presente une chimioselectivite remarquable.
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21

SEGUINEAU, PASCALE. "Les reactions de wittig et wittig-horner en milieu protique peu basique." Nantes, 1989. http://www.theses.fr/1989NANT2014.

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La reaction de wittig-horner realisee dans des conditions douces (milieu aqueux peu basique) a l'aide de composes dicarbonyles permet d'acceder par bisaldolisation a des cyclenols alpha -fonctionnalises. Grace a cette technique douce, la reaction de wittig-horner est chimioselective et ne s'effectue que sur les sites carbonyles tres actifs (aldehydes)
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22

Rovira, Coll Mireia. "Reaction mechanisms involved in cross coupling processes catalysed by copper and nickel." Doctoral thesis, Universitat de Girona, 2017. http://hdl.handle.net/10803/403434.

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Organometallic aryl-CuIII species have been proposed as key intermediates in Ullmann-type reactions. However, such species have long remained elusive and mechanistic investigations of a plausible catalytic cycle remained ambiguous and speculative. The first part of this thesis deals with the reactivity of well-defined aryl-CuIII macrocyclic complex in presence of activated methylenes (Hurtley-type coupling) and terminal acetylenes (Stephens-Castro-type coupling). The subsequent part deals with the synthesis and fully characterization of well-defined aryl-NiII complex, which is analogous to aryl-CuIII complex. The strength of the Ni-C bond precludes their direct reactivity with nucleophiles via reductive elimination. Nevertheless, we have proved their reactivity in the presence of a 2 e- redox oxidant as an electrophilic CF3+ source. In the last part, we turned our attention to the standard Cu-catalyzed Ullmann-type reactions by studying the effect of the ligand choice on the chemoselectivity of a multiple combinations of amides, amines and phenols in competitive reactions
Les espècies aril-CuIII han estat proposades com les espècies a través de les quals operen els acoblaments tipus Ullmann. No obstant, aquestes espècies són molt reactives i difícilment detectables en els processos fonamentals que governen aquests acoblaments. La primera part d’aquesta tesi es centra en l’estudi de la reactivitat de complexes ben definits aril-CuIII davant de metilens actius (Reacció de Hurtley) i acetilens terminals (Reacció de Stepens-Castro). La següent part es centra en la síntesi i caracterització de complexes ben definits aril-NiII, anàlegs als de coure. La curta distància de l’enllaç Ni-C dissenteix la seva reactivitat davant diversos nucleòfils via eliminació reductiva. Per contra, aquestes espècies són reactives en presència de fonts electrofíliques de CF3+. En l’última part, ens centrem en l’estudi de les propietats estèriques dels lligands auxiliars coordinats al centre de coure i la selectivitat que presenten envers diferents nucleòfils en els sistemes estàndards de tipus Ullmann
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23

Prat, Denis. "Epoxydations stereoselectives d'alcools olefiniques par l'eau oxygene a 30% catalysees par l'acide tungstique en milieu tamponne." Paris 6, 1988. http://www.theses.fr/1988PA066493.

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Apres discussion de la nature des especes pertungstiques dans les conditions de catalyse, on interprete les stereoselectivites en supposant l'alcool olefinique ligand apical d'un peroxytungstate de structure bipyramide pentagonale, et une attaque perpendiculaire de l'olefine dans l'axe d'une liaison o-o; le mecanisme de la formation de l'enone est discute en faisant intervenir une espece vooh dans laquelle l'alcool olefinique est ligand du tungstene
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24

Pham, Thi-Nhan Nguyen. "Thio-rearrangement de claisen : facilite, reversibilite, synthese de composes thiocarbonyles." Caen, 1987. http://www.theses.fr/1987CAEN2045.

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25

Figadère, Bruno. "Les composes organomanganeux mixtes : addition 1-2 selective sur des aldehydes ou des cetones portant un groupe fonctionnel, enolisation regioselective de cetones : application en synthese." Paris 6, 1987. http://www.theses.fr/1987PA066371.

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Les reactifs organomanganeux rmnx(x=cl, br, i; r=n-, sec- t-alkyl, alcenyl, aryl, alcynyl) s'additionnent aux aldehydes et cetones fonctionnels pour donner selectivement les alcools correspondant avec d'excellents rendements. Les reactifs rmnz(z=nphme) enolisent les cetones avec une excellente regioselectivite. Les enolates manganeux ainsi prepares sont tres aisement acyles, silyles, alkyles, hydroxyalkyles, avec des rendements de 60% a 90%, a la temperature ambiante
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26

Hlimi, Fouzia. "Cycloaddition de diarylnitrilimines sur des dérivés de la benzodioxine 1,4 et de la benzoxazine-1,4 : regiochimie de la réaction sur un alcene portant un groupe donneur et un groupe accepteur sur la même extrêmité." Besançon, 1987. http://www.theses.fr/1987BESA2018.

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La cycloaddition dipolaire 1,3 des diarylnitrilimines sur le benzodioxinne-1,4 carboxylate-2 d'ethyle conduit a des cycloadduits qui apres ouverture donnent des derives de l'aryloxy-4 diphenyl-1,3 pyrazole qui ne sont pas accessibles par une methode classique de synthese de pyrazoles
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27

Gil, Filipe Carlos Teixeira. "Chemoselectivity of Immobilized Transition Metal Catalysts: a Computational Study." Tese, 2014. https://repositorio-aberto.up.pt/handle/10216/76131.

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28

Gil, Filipe Carlos Teixeira. "Chemoselectivity of Immobilized Transition Metal Catalysts: a Computational Study." Doctoral thesis, 2014. https://repositorio-aberto.up.pt/handle/10216/76131.

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29

Tardiff, Bennett Joseph. "PALLADIUM-CATALYZED AMINE SYNTHESIS: CHEMOSELECTIVITY AND REACTIVITY UNDER AQUEOUS CONDITIONS." 2012. http://hdl.handle.net/10222/14784.

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The palladium-mediated cross-coupling of aryl electrophiles and amines (Buchwald-Hartwig amination) has become a widely used method of constructing arylamine frameworks. A crucial aspect of the advancement of this chemistry has been the design of ancillary ligands that are able to promote enhanced reactivity in challenging amination reactions. Despite significant ligand development within the field, challenges in this chemistry remain. Chemoselective aminations, wherein one amine substrate undergoes preferential arylation in the presence of multiple reactive amines has remained an underexplored area of Buchwald-Hartwig amination chemistry. This thesis describes the use of [Pd(cinnamyl)Cl]2 and N-[2-di(1-adamantylphosphino)phenyl]morpholine (Mor- DalPhos) in an extensive study of chemoselective Buchwald-Hartwig aminations, with 62 examples of structurally diverse di-, tri-, and tetraamines obtained in synthetically useful yields at reasonable catalyst loadings (1-5 mol % Pd). The coordination chemistry of [(Mor-DalPhos)Pd] species was also explored, as were complementary chemoselective aminations with the isomeric p-Mor-DalPhos ligand, leading to divergent product formation in some instances. The same [Pd(cinnamyl)Cl]2/Mor-DalPhos catalyst system used in the chemoselectivity study was also employed in a series of Buchwald-Hartwig aminations conducted under aqueous and solvent-free conditions, another underexplored area of this chemistry. A total of 52 amine products were isolated using these methodologies, moderate catalyst loadings (3 mol % Pd), and without the use of any additional additives, co-solvents, or rigorous exclusion of air. The synthesis of low-coordinate palladium complexes featuring both NHC and dialkylchlorophosphine ligands is also discussed herein. These complexes are prepared via a previously unreported and straightforward methodology involving an unusual net PCl bond reductive elimination, and represent a potential new class of pre-catalysts forpalladium-mediated reactions.
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30

Huang, Ching-Chun, and 黃靖鈞. "Chemoselectivity in Heterobimetallic Palladium-Cobalt Tetraacetate Catalyzed Intramolecular C-H Bond Nitrene Insertion of Sulfamate Esters." Thesis, 2013. http://ndltd.ncl.edu.tw/handle/99042310562377945650.

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碩士
中原大學
化學研究所
101
The purpose of this research is to study the chemoselectivity of intramolecular nitrene insertion of sulfamate ester catalyzed by PdCo (OAc) 4 which was synthesized from Pd(OAc) 2 and Co(OAc) 2. In this study, sulfamate ester compounds 9-13 were used as reactants, for the PdCo(OAc)4 catalyzed amination reaction of C-H bond. The chemoselectivity was analyzed from the product distribution of resulting oxathiazinane compounds.
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31

Nath, Dinesh. "Metalated Nitriles: Ligand Exchange and Copper-Catalyzed Reactions." 2013. http://digital.library.duq.edu/u?/etd,162308.

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This thesis describes new methods of carbon-carbon bond formation using metalated nitriles generated via metal exchange reactions. Sulfinylnitriles undergo a sulfinyl-metal exchange to yield lithiated, magnesiated and zincated nitriles, which can trap a range of electrophiles. The sulfinyl-metal exchange is effective with vinylic, quaternary and tertiary substitution patterns and addresses the long-standing problem of alkylating secondary nitriles. This method was then further extended to other oxidation states of sulfur, namely sulfonyl-metal exchange and relatively unknown sulfide-metal exchange. The sulfide metal exchange overcomes the problem related to the propensity of highly substituted sulfinylnitriles to eliminate. Sulfide-metal exchange is synthetically attractive because of the numerous methods for generating arylsulfides and the high tolerance of arylsulfides to numerous reagents. <br>A copper-catalyzed arylation reaction of aryl iodides and metalated nitriles was developed using catalytic Cu (I) and an amine ligand. A proof of principle has been established, providing a sound basis for developing the reaction. A new strategy has been developed for alkylation of alkenenitrile using LDA as base in presence of catalytic CuCN. Subsequent trapping with an electrophile, affords alkylated alkenenitriles in which the olefin is no longer in conjugation with the nitrile. <br>The distinct structural differences between N- & C-metalated nitriles have been harnessed in a series of chemoselective alkylations. Lithiated nitriles are found to be particularly reactive toward alkyl halides whereas magnesiated nitriles react selectively with oxygenated electrophiles. Using this strategy allows chemoselective alkylation of metalated nitriles.
Bayer School of Natural and Environmental Sciences;
Chemistry and Biochemistry
PhD;
Dissertation;
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32

Chen, Airu, and 陳愛如. "Applying Free Radical SH2' Reaction To The Free Radical Addition Cyclization Reaction To Investigate The Chemoselectivity And Steroselectivity." Thesis, 2012. http://ndltd.ncl.edu.tw/handle/92206920319981756440.

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碩士
義守大學
生物技術與化學工程研究所
100
In recent years, the application of Free Radicals in Organic Synthesis was attractive, especially in chemoselectivity and stereoselectivity. The concerted mechanism of the free radical SH2' reaction when the leaving group of the substrate was halogen (Br, Cl), was discovered by this laboratory. The free radical addition to the double bond, the leaving group rupture and one bond forming were occurred simultaneously in the free radical SH2' reaction. The two p orbitals of two carbons must be parallel in order to form the bond, therefore, the orientation of the reaction somehow would be limited, and this might be helpful to promote the stereoselectivity of the reaction. The stereo-selectivity of free radical addition cyclization reaction might be raised if the free radical SH2' reaction is introduced to this reaction. Using tert-butyl radical with asymmetric diene [(2-chloropropenyl)-(1-Bromo-2-butenyl) ether、(3-acryl)-(2-chloromethylpropenyl) ether] to conduct free radical addition cyclization reaction, study the regio-selectivity、stereo-selective and addition cyclization path when the free radicals addition cyclization reaction, its free radical addition to different position on the double bond, and confirm the stereo structure by 1H NMR、13C NMR、DEPT、gCOSY、NOESY、gHSQC和gHMBC of nuclear magnetic resonance instrument.
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33

Liptak, Vincent Paul. "Investigation of the chemoselectivity and efficiency of the benzannulation reaction of electron poor aryl Fischer carbene complexes : synthetic studies toward (+)-olivn /." 2000. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:9978043.

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34

Davi, Michaël. "Développement d'une nouvelle méthodologie d'oléfination catalysée par les complexes de cuivre : applications dans des réactions en tandem." Thèse, 2008. http://hdl.handle.net/1866/6553.

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35

Pelletier, Guillaume. "Synthèse stéréosélective de pipéridines et activation électrophile chimiosélective d’amides en présence de dérivés de la pyridine." Thèse, 2013. http://hdl.handle.net/1866/10512.

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L’importance des produits naturels dans le développement de nouveaux médicaments est indéniable. Malheureusement, l’isolation et la purification de ces produits de leurs sources naturelles procure normalement de très faibles quantités de molécules biologiquement actives. Ce problème a grandement limité l’accès à des études biologiques approfondies et/ou à une distribution sur une grande échelle du composé actif. Par exemple, la famille des pipéridines contient plusieurs composés bioactifs isolés de sources naturelles en très faible quantité (de l’ordre du milligramme). Pour pallier à ce problème, nous avons développé trois nouvelles approches synthétiques divergentes vers des pipéridines polysubstituées contenant une séquence d’activation/désaromatisation d’un sel de pyridinium chiral et énantioenrichi. La première approche vise la synthèse de pipéridines 2,5-disubstituées par l’utilisation d’une réaction d’arylation intermoléculaire sur des 1,2,3,4-tétrahydropyridines 2-substituées. Nous avons ensuite développé une méthode de synthèse d’indolizidines et de quinolizidines par l’utilisation d’amides secondaires. Cette deuxième approche permet ainsi la synthèse formelle d’alcaloïdes non-naturels à la suite d’une addition/cyclisation diastéréosélective et régiosélective sur un intermédiaire pyridinium commun. Finalement, nous avons développé une nouvelle approche pour la synthèse de pipéridines 2,6-disubstituées par l’utilisation d’une réaction de lithiation dirigée suivie d’un couplage croisé de Negishi ou d’un parachèvement avec un réactif électrophile. Le développement de transformations chimiosélectives et versatiles est un enjeu crucial et actuel pour les chimistes organiciens. Nous avons émis l’hypothèse qu’il serait possible d’appliquer le concept de chimiosélectivité à la fonctionnalisation d’amides, un des groupements le plus souvent rencontrés dans la structure des molécules naturelles. Dans le cadre précis de cette thèse, des transformations chimiosélectives ont été réalisées sur des amides secondaires fonctionnalisés. La méthode repose sur l’activation de la fonction carbonyle par l’anhydride triflique en présence d’une base faible. Dans un premier temps, l’amide ainsi activé a été réduit sélectivement en fonction imine, aldéhyde ou amine en présence d’hydrures peu nucléophiles. Alternativement, un nucléophile carboné a été employé afin de permettre la synthèse de cétones ou des cétimines. D’autre part, en combinant un amide et un dérivé de pyridine, une réaction de cyclisation/déshydratation permet d’obtenir les d’imidazo[1,5-a]pyridines polysubstituées. De plus, nous avons brièvement appliqué ces conditions d’activation au réarrangement interrompu de type Beckmann sur des cétoximes. Une nouvelle voie synthétique pour la synthèse d’iodures d’alcyne a finalement été développée en utilisant une réaction d’homologation/élimination en un seul pot à partir de bromures benzyliques et allyliques commercialement disponibles. La présente méthode se distincte des autres méthodes disponibles dans la littérature par la simplicité des procédures réactionnelles qui ont été optimisées afin d’être applicable sur grande échelle.
The importance of natural products in the development of new drugs is undeniable. Unfortunately, the isolation and purification of those products from their natural sources provides normally very small amounts of the desired bioactive molecules. Consequently there is largely limited access to in-depth biological studies and/or to the large scale distribution of the bioactive compound. For example, the piperidine family contains a large diversity of bioactive compounds isolated from natural sources in very limited quantities (on the order of milligram scale). To address the issue, we have developed three new divergent synthetic approaches towards polysubstituted piperidines containing an activation/dearomatization sequence from a chiral and enantioenchired pyridinium salt. The first approach aims towards the synthesis of 2,5-disubstituted piperidines by the use of an intermolecular arylation reaction on 2-substituted 1,2,3,4-tetrahydropyridines. Then, we have developed a synthetic method for indolizidines and quinolizidines starting from secondary amides. The second approach leads to the formal synthesis of non-natural alkaloids via a highly diastereoselective and regioselective addition/cyclization from a common pyridinium intermediate. Finally, we have found a new approach for the synthesis of 2,6-disubstituted piperidines by the use of a directed lithiation sequence followed by either a Negishi cross-coupling reaction or a quench with an electrophilic reagent. The development of highly chemoselective and versatile transformations are crucial to organic chemists. We have issued the hypothesis that it could be possible to apply the chemoselectivity concept towards the functionalization of amides, one of the most encountered subunits in the structures of natural products. In the specific context of the thesis, the highly chemoselective transformations are realized on functionalized secondary amides. The method relies on the activation of the carbonyl function of the amide by triflic anhydride in presence of a weak base. Firstly, the activated amide can be selectively reduced to imine, aldehyde, or amine oxidation state in the presence of a poorly nucleophilic hydride source. Alternatively, a carbon nucleophile could also be employed in order to allow the synthesis of ketones or ketimines. By combining an amide with a pyridine derivative a cyclization/dehydration reaction was used for the synthesis of polysubstituted imidazo[1,5-a]pyridines. Moreover, we have briefly applied the activation conditions to the interrupted Beckmann rearrangement of ketoximes. We have finally developed a new synthetic pathway for iodoalkynes by using a one-pot homologation/elimination reaction from commercially available benzylic and allylic bromides. The present method is distinctively different from literature precedents by the simplicity of the reaction procedures and purifications which were optimized in order to be applied to large scale synthesis
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