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Dissertations / Theses on the topic 'Allyic substitution'

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Published: 2 November 2024
Last updated: 19 July 2025

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1

Yu, Xiaodan. "New functionalized alkylidenecyclobutanes : multicomponent synthesis and applications." Electronic Thesis or Diss., université Paris-Saclay, 2024. http://www.theses.fr/2024UPASF034.

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Les dérivés du cyclobutane sont devenus de plus en plus importants en tant que blocs de construction moléculaires en raison de leur contrainte cyclique inhérente et de la modification sélective de leurs structures qui peuvent être utilisées de manière stratégique dans la synthèse organique. Les cycles cyclobutane apparaissent également dans les structures moléculaires d'un large panel de molécules naturelles et synthétiques qui présentent des activités biologiques intéressantes. Au sein de cette grande famille, les sous-unités alkylidènecyclobutane sont rencontrées dans des produits naturels,
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2

Xie, Jianing. "Advancing Pd-catalyzed Stereoselective Allylic Substitution Reactions." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670221.

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Aquesta tesi doctoral se centra principalment en el desenvolupament de nous mètodes catalítics (dòmino) basats en la substitució al·lílica catalitzada per Pd per a la síntesi estereoselectiva de petites molècules funcionals i heterocicles utilitzant un disseny detallat de lligants i substrats. Aquesta tesi està organitzada en cinc capítols: el primer capítol és una introducció general sobre els aspectes bàsics de la química al·lílica. El segon capítol il·lustra el primer mètode general per a la preparació d'èters arílics al·lílics terciaris enantioenriquits mitjançant una eterificación regio-
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3

Clizbe, Elizabeth Adair. "Assymmetric transition metal-catalyzed allylic substitution reactions." Thesis, University of Liverpool, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.539737.

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4

Chen, Bocheng. "Double Allylic Substitution of Alkenyl vic-Diol." Electronic Thesis or Diss., université Paris-Saclay, 2024. http://www.theses.fr/2024UPASF051.

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La substitution allylique est reconnue comme l'un des outils les plus puissants en synthèse organique pour la construction de liaisons C-C et C-hétéroatome. L'exemple le plus connu est la réaction de Tsuji-Trost, l'allylation de nucléophiles mous catalysée par le palladium, qui a été largement étudiée. Une séquence de double substitution allylique sur un substrat simple pourrait permettre de générer rapidement de la complexité moléculaire en introduisant deux nucléophiles dans une réaction monotope. Cependant, ce type de réaction a rarement été rapportée en raison des difficultés de contrôle à
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5

Cai, Aijie. "Pd-catalyzed Allylic Substitution for Construction of Quaternary Stereocenters." Doctoral thesis, Universitat Rovira i Virgili, 2019. http://hdl.handle.net/10803/668819.

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Des del primer treball inicial de Tsuji i Trost, hi ha hagut un ràpid progrés durant les últimes dècades en el desenvolupament de lligands quirals i l'abast de reacció dels electròfils i nucleòfils aplicables en reaccions de substitució al·lílica catalitzades per Pd. A més, s'han utilitzat reaccions de substitució al·lílica asimètriques asimètriques catalitzades per Pd en la síntesi total d'una varietat de molècules quirals complexes, proporcionant una evidència sòlida de la utilitat de la metodologia AAA en el control tant de la regio com de l'enantio-selectivitats. Malgrat els nombrosos aven
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6

Takeda, Momotaro. "Copper-Catalyzed Asymmetric Allylic Substitution with Organo- and Silylboronates." 京都大学 (Kyoto University), 2014. http://hdl.handle.net/2433/188504.

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7

Baldwin, I. Craig. "New methodology involving allylic substitution and conjugate addition reactions." Thesis, Loughborough University, 1996. https://dspace.lboro.ac.uk/2134/27583.

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Chapter one reviews routes to the generation of α-aminophosphonates and α-aminophosphonic acids. These biologically important compounds are synthesised in both racemic and enantiomerically enriched forms. The second chapter describes the results of conjugate addition reactions of lower order cuprates to diethylvinylphosphonate followed by an electrophilic quench to give a range of alkylphosphonates. The third and fourth chapters are concerned with the generation of enantiomencally enriched α-aminophosphonates and α-aminoesters via palladium catalysed allylic substitution reactions With allyl a
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8

Dawson, Graham John. "Studies on the stereoselective palladium-catalysed allylic substitution reaction." Thesis, Loughborough University, 1995. https://dspace.lboro.ac.uk/2134/31866.

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This thesis contains the preparation of a new design of ligand for the palladium catalysed allylic substitution reaction. The phosphine oxazoline ligands detailed in the thesis give high levels of enantiocontrol when used in conjunction with symmetrical allyl systems in the palladium catalysed allylic substitution reaction. For unsymmetrical allyl systems the palladium catalysed allylic substitution process proceeds with complete regiocontrol and high levels of stereocontrol are again observed. The products from the palladium catalysed allylic substitution reaction can be readily converted to
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9

Tosatti, Paolo. "Metal-catalysed asymmetric allylic substitution reactions for array synthesis." Thesis, University of Leeds, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.540583.

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10

Kawatsura, Motoi. "Palladium-Catalyzed Allylic Substitution with a Monodentate Phosphine Ligand." 京都大学 (Kyoto University), 1998. http://hdl.handle.net/2433/157157.

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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<br>Kyoto University (京都大学)<br>0048<br>新制・課程博士<br>博士(理学)<br>甲第7163号<br>理博第1937号<br>新制||理||1043(附属図書館)<br>UT51-98-G92<br>京都大学大学院理学研究科化学専攻<br>(主査)教授 林 民生, 教授 鈴木 仁美, 教授 大須賀 篤弘<br>学位規則第4条第1項該当
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11

Ceban, Victor. "New methodologies in asymmetric allylic substitution and organocascade reactions." Thesis, University of Southampton, 2015. https://eprints.soton.ac.uk/397983/.

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Asymmetric organocatalysis and organometallic catalysis are rapidly developing. The first catalytic process can be traced back in the XIX century. Since then, research in the field of catalysis grew, especially in the last decades exponentially. Four projects involving organocatalysis are described in this thesis: “Highly enantioselective addition of anthrones to MBH-carbonates”, “Synergistic catalysis: Highly diastereoselective benzoxazole addition to Morita-Baylis-Hillman carbonates”, “Three-component diastereoselective cascade synthesis of thiohydantoins” and “Highly diastereoselective synt
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12

Popa, Dana Madeleine. "Modular phosphinooxazolines: synthesis and evaluation in allylic substitutions." Doctoral thesis, Universitat Rovira i Virgili, 2008. http://hdl.handle.net/10803/9025.

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La reacción de substitución alílica asimétrica representa un método importante para la generación de enlaces C-C y C-N de forma estereoselectiva (Esquema 1).<br> Las fosfinooxazolinas (Figura 1) fueron descritas originalmente en 1993 por Pfaltz Williams y Helmchen1 de simultáneamente y han sido utilizadas en múltiples ejemplos de sustituciones alílicas enantioselectivas sobre una gran diversidad de sustratos.<br> En el primer capitulo de la Tesis, se recoge la síntesis y caracterización de una familia altamente modular de complejos de paladio-fosfinooxazolina. La metodología de síntesis empl
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13

Béton, Didier. "Synthesis of new phosphorus amidite ligands : iridium-catalyzed allylic substitution /." Heidelberg, 2008. http://opac.nebis.ch/cgi-bin/showAbstract.pl?sys=000253233.

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14

Litvinov, Alexander E. "Ortho-diphenylphosphanylbenzoyl-directed Palladium catalyzed allylic substitution with soft nucleophiles." [S.l. : s.n.], 2008. http://nbn-resolving.de/urn:nbn:de:bsz:25-opus-61462.

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15

Perrone, Sylvie. "Copper(I)-mediated anti-SN2' allylic substitution reactions with diorganozinc reagents." Diss., [S.l.] : [s.n.], 2006. http://edoc.ub.uni-muenchen.de/archive/00006218.

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16

Cheng, Xiaohui. "Transition metal catalysed homogeneous hydroamination, allylic substitution and transfer hydrogenation reactions." Thesis, King's College London (University of London), 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.410013.

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17

Baxendale, Ian Richard. "An investigative study into group 6 metal catalysed allylic substitution reactions." Thesis, University of Leicester, 1999. http://hdl.handle.net/2381/33907.

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We have shown that a number of molybdenum(II) and tungsten(II) complexes are capable of catalysing the C-C bond forming allylic substitution reaction with silyl enol ethers derived from dicarbonyls or simple ketones, aldehydes, and esters as nucleophiles under mild conditions (rt, 1-2 h). Mechanistic and stereochemical experiments are indicative of a Lewis-acid catalysed process. The research was successful in identifying an number of key catalyst structures and properties for our continued investigation into M(II) catalysts. We have subsequently developed a catalytic system based on the chemi
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18

Le, Chi. "Efforts Toward Improved Allylic Substitution via Pd-Catalyzed C-H Activation." The Ohio State University, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=osu1396436482.

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19

Spangenberg, Thomas. "Synthesis of biomolecules using directed allylic substitution, multicomponent reaction and hydroformulation." Université Louis Pasteur (Strasbourg) (1971-2008), 2008. http://www.theses.fr/2008STR13250.

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L'économie d'atomes est un enjeu majeur dans le domaine de la synthèse organique. Dans cette optique, la préparation de cibles d'intérêts biologiques (amino-acides, alcaloïdes) par de nouvelles stratégies de synthèse attire en permanence l'attention des chimistes. [. . . ]<br>Atomökonomische Reaktionen gewinnen in der organische Synthese eine zunehmend an Bedeutung, nicht nur bei der Herstellung einfacher Moleküle sondern auch für strukturell aufwendige und biologisch hochwirksame Moleküle wie z. B. Alkaloide und nicht natürliche Aminosäuren. [. . . ]
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20

Hagelin, Helena. "Palladium-catalyzed aromatic coupling and allylic substitution : an experimental and theoretical study /." Stockholm, 1999. http://www.lib.kth.se/abs99/hage0528.pdf.

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21

Jiang, Xingyu. "Iridium-Catalyzed Asymmetric Allylic Substitution Reactions with Unstabilized Enolates and Prochiral Enolates." Thesis, University of California, Berkeley, 2019. http://pqdtopen.proquest.com/#viewpdf?dispub=13422366.

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<p>The following dissertation discuss the development of iridium-catalyzed asymmetric allylic substitution reactions with unstabilized enolates and prochiral enolates. These reactions include the enantioselective allylic substitutions with silyl ketene acetals, diastereo- and enantioselective allylic substitutions with ?-alkoxy ketones, and stereodivergent allylic substitutions with aryl acetic acid esters, azaaryl acetamides and azaaryl acetates. Chapter 1 provides a brief overview of transition-metal-catalyzed asymmetric allylic substitutions with enolates. This overview focused on the mech
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22

Norinder, Jakob. "Asymmetric Synthesis and Mechanistic Studies on Copper(I)-Catalyzed Substitution of Allylic Substrates." Doctoral thesis, Stockholm : Department of Organic Chemistry, Stockholm University, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-1031.

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23

Stranne, Robert. "Investigation of Symmetry and Electronic Effects in Asymmetric Palladium-Catalysed Allylic Substitutions." Doctoral thesis, KTH, Chemistry, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3283.

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24

O'Connor, Ryan. "Rhodium-catalysed allylic substitution with unstabilised carbon nucleophiles : asymmetric construction of carbon-carbon bonds." Thesis, University of Liverpool, 2013. http://livrepository.liverpool.ac.uk/17253/.

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The controlled formation of carbon-carbon bonds is the bedrock of organic chemistry, with the asymmetric construction of stereogenic carbon-carbon bonds remaining a key motivation for the development of novel synthetic methodologies. Transition metal catalysis provides an important strategy in the arsenal of the modern synthetic chemist. While there is a plethora of transition metal-catalysed cross-couplings for the formation of sp2-sp2 and achiral sp2-sp3 carbon bonds, there are relatively few methodologies for the selective formation of stereogenic sp-sp3, sp2-sp3 and sp3-sp3 carbon-carbon b
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25

Zhou, Yuebiao. "New Strategies for the Development of Catalytic Regio- and Enantioselective Allylic Substitution and Conjugate Addition Reactions:." Thesis, Boston College, 2020. http://hdl.handle.net/2345/bc-ir:108959.

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Thesis advisor: Amir H. Hoveyda<br>Chapter 1. Catalytic SN2”-Selective and Enantioselective Substitution Reactions. The first broadly applicable strategy for SN2”-selective and enantioselective catalytic allylic substitution will be presented. It will be shown that transformations can be promoted by 5.0 mol% of a sulfonate-containing NHC–Cu complex (NHC = N-heterocyclic carbene), and may be carried out by the use of a commercially available allenyl–B(pin) (pin = pinacolato) or a readily accessible silyl protected propargyl–B(pin). Products bearing a 1,3 diene, a silyl allenyl or a propargyl mo
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26

Müller, Constanze Annelie. "Mass spectrometric screening of chiral catalysts by monitoring the back reaction: Palladium-catalysed allylic substitution." Göttingen Cuvillier, 2008. http://d-nb.info/989139719/04.

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27

Müller, Constanze A. "Mass spectrometric screening of chiral catalysts by monitoring the back reaction : palladium-catalysed allylic substitution /." [S.l.] : [s.n.], 2008. http://edoc.unibas.ch/diss/DissB_8322.

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28

Olsson, Vilhelm. "Development of New Synthetic Routes to Organoboronates by Catalytic Allylic Substitution and C-H bond Functionalization." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-27753.

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This thesis describes the development of new catalytic methods for the synthesis and application of organometallic reagents, mainly focusing on allylboronic acid derivatives. Thus, palladium pincer-complex catalysis has been applied for extending the scope of palladiumcatalyzed borylation reactions in the synthesis of regio- and stereodefined functionalized allylboronic acid derivatives. These novel allylboronic acids were also employed as substrates in palladium catalyzed regioselective coupling reactions with iodobenzenes. We have also developed a new one-pot sequence based on preparation of
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29

Selim, Khalid Bashir Shaaban. "Development of chiral ligand-copper(1)-catalyzed asymmetric conjugate addition and allylic substitution with organometallic reagents." 京都大学 (Kyoto University), 2009. http://hdl.handle.net/2433/126604.

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30

McGrath, Kevin Patrick. "Enantioselective Methods for Allylic Substitution and Conjugate Addition Reactions Catalyzed by N-Heterocyclic Carbene-Copper Complexes." Thesis, Boston College, 2016. http://hdl.handle.net/2345/bc-ir:106792.

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Thesis advisor: Amir H. Hoveyda<br>Chapter 1 Catalytic Enantioselective Addition of Organoaluminum Reagents Catalytic methods involving the enantioselective addition of both commercially available as well as in situ generated organoaluminum reagents are reviewed. An overview of additions to aldehydes, ketones, and imines is provided as well as the difficulties and limitations of such transformations. Furthermore, additions to unsaturation adjacent to a leaving group to form a new stereogenic center are examined. Finally, conjugate addition reactions wherein an organoaluminum reagent is added t
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31

Gao, Fang. "Copper-Catalyzed Enantioselective Allylic Substitution Reactions with Organoaluminum and Boron Based Reagents Promoted by Chiral Sulfonate Bearing N-Heterocyclic Carbenes." Thesis, Boston College, 2013. http://hdl.handle.net/2345/bc-ir:101227.

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Thesis advisor: Amir H. Hoveyda<br>Chapter 1. A Review of Catalytic Enantioselective Allylic Substitution (EAS) with Chiral Sulfonate Containing N-heterocyclic Carbenes (NHC). A comprehensive review of enantioselective allylic substitution reactions, which are promoted by a chiral N-heterocyclic carbene metal complex that features a unique sulfonate motif, is provided in this chapter. Reactions are classified into two categories. One class of transformations is catalyzed by a series of easily modifiable sulfonate bearing NHC-Cu complexes, with which a range of nucleophilic organometallic reage
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32

Soorukram, Darunee. "Copper(I)-mediated regio- and stereoselective allylic substitutions and their applications to natural product syntheses." Diss., [S.l.] : [s.n.], 2006. http://edoc.ub.uni-muenchen.de/archive/00006234.

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33

Bricout, Hervé. "Isomérisation et substitution nucléophile en série allylique catalysées par des complexes phosphorés du nickel." Lille 1, 1997. https://pepite-depot.univ-lille.fr/LIBRE/Th_Num/1997/50376-1997-21.pdf.

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Le complexe ni(dppb)#2, forme en solution par combinaison du nickelbis(cycloocta-1,5-diene) avec le ligand 1,4-bis(diphenylphosphino)butane (dppb), présente des propriétés catalytiques intéressantes dans la chimie des dérives allyliques: associe à l'acide trifluoroacetique, ce complexe catalyse l'isomerisation du géraniol en citronellal ; les meilleurs rendements sont obtenus en présence de butane-1,2-diol. Utilise sans cocatalyseur acide, le même complexe est actif dans l'allylation de nucléophiles mous par des composes allyliques oxygènes, azotes, ou dérives du 2-allylmalonate de diméthyle.
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34

Oliver, Samuel. "Rhodium-catalysed allylic substitution with an acyl anion equivalent : asymmetric construction of acyclic quaternary carbon stereogenic centres." Thesis, University of Liverpool, 2012. http://livrepository.liverpool.ac.uk/8433/.

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The asymmetric construction of substituted carbonyl compounds, particularly those containing α-quaternary carbon stereogenic centres, remains a significant area of interest in organic chemistry. This can largely be attributed to the ubiquity and versatility of these compounds as synthetic intermediates, and the presence of such motifs in a range of biologically active pharmaceutical agents and natural products. In this context, the transition metal-catalysed allylic substitution provides an extremely powerful tool for the asymmetric construction of a range of C-C, C-N and C-O bonds, and has fo
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35

Larsson, Johanna M. "Transition metal-catalyzed allylic and vinylic functionalization : Method development and mechanistic investigations." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-89524.

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The use of small molecule building blocks in, for example, pharmaceutical research and new material development, creates a need for new and improved organic synthesis methods. The use of transition metals as mediators and catalysts opens up new reaction pathways that have made the synthesis of completely new compounds possible as well as greatly improved the synthetic routes to known compounds. Herein, the development of new metal-mediated and catalyzed reactions for construction of vinylic and allylic carbon-carbon and carbon-heteroatom bonds is described.  The use of iodonium salts as coupli
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36

Arnold, Jeffrey Scott. "Rhodium-catalyzed asymmetric amination of trichloroacetimidates with application to nitrogen heterocycle synthesis." Diss., University of Iowa, 2014. https://ir.uiowa.edu/etd/4565.

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Chiral quaternary centers possessing a bond to nitrogen are an important class of amine compounds, however, methods for their enantioselective preparation remain sparse. The focus of my graduate research described herein has been the development of a novel rhodium-catalyzed regio- and enantioselective allylic aryl amination of tertiary trichloroacetimidates for the synthesis of amine-bearing quaternary centers (also termed α,α-disubstituted amines). Prior to our work, allylic carbonates and acetates had been successfully utilized in transition-metal catalyzed substitution reactions with anilin
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37

Guillarme, Stéphane. "Synthèse de nouveaux nucléosides acycliques : étude de la réaction de substitution allylique sur des dérivés cyclobuténiques : approche vers la synthèse de nucléosides cyclobuténiques." Le Mans, 2002. http://cyberdoc.univ-lemans.fr/theses/2002/2002LEMA1009.pdf.

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Lors de notre travail, nous nous sommes intéressés à la synthèse de nouveaux nucléosides acycliques et carbocycliques à propriétés antivirales et anticancéreuses potentielles. Dans la première partie de notre étude, les nucléosides acycliques, analogues du penciclovir, ont été préparés par introduction des bases azotées par une réaction de Michael. Cette stratégie, très peu utilisée, a permis également l'incorporation de bases déazas qui sont peu nucléophiles et souvent introduites par construction. La réaction des bases sur les accepteurs de Michael s'est effectuée avec une bonne régiosélecti
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Shi, Ying. "Copper-catalyzed Enantioselective Allylic Substitutions and Conjugate Additions Promoted by Chiral Sulfonate- or Alkoxy-containing N-heterocyclic Carbenes." Thesis, Boston College, 2017. http://hdl.handle.net/2345/bc-ir:107648.

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Thesis advisor: Amir H. Hoveyda<br>Chapter 1. A Review of Sulfonate-Containing NHC Ligands in Copper-Catalyzed Enantioselective Transformations—Maneuvering Selectivities in Tight Space. A comprehensive review of enantioselective copper-catalyzed transformations, which are promoted by a chiral N-heterocyclic carbene metal complex that features a unique sulfonate motif, is provided in this chapter. Reactions have been categorized into four sets: allylic substitutions conjugate additions, Cu-B additions alkenes and multicomponent reactions. The mechanistic scenarios provided by DFT calculations a
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39

Defieber, Christian Volker. "Chiral olefins as novel ligands in asymmetric synthesis and the development of water and ammonia equivalents in iridium-catalyzed allylic substitution /." Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17170.

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40

Mandai, Kyoko. "Cu-Catalyzed Enantioselective Allylic Substitutions with Organomagnesium and Organoaluminum Reagents Promoted by N-Heterocyclic Carbenes for the Formation of Quaternary Stereogenic Centers." Thesis, Boston College, 2010. http://hdl.handle.net/2345/1329.

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Thesis advisor: Amir H. Hoveyda<br>Chapter One: An overview of Cu-catalyzed enantioselective allylic substitutions with organometallic reagents. Chapter Two: Development of Cu-catalyzed enantioselective allylic alkylations of allylic chlorides with Grignard reagents for the formation of all-carbon quaternary stereogenic centers is disclosed. Chapter Three: Development of Cu-catalyzed enantioselective allylic substitutions of allylic phosphates with alkyl, aryl, and heterocyclic aluminum reagents for the formation of quaternary stereogenic centers is discussed<br>Thesis (MS) — Boston College, 2
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41

Thomasset, Amélia. "Synthèse de carbènes N-hétérocycliques chiraux et applications en catalyse asymétrique." Phd thesis, Université Paris Sud - Paris XI, 2013. http://tel.archives-ouvertes.fr/tel-01070636.

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Ce travail de thèse porte dans un premier temps sur la synthèse de nouveaux sels d'azolinium chiraux précurseurs de carbènes N-hétérocycliques. Deux nouvelles familles de sels ont été préparées à partir de la L-proline. Nous avons pu caractériser les NHC issus de ces sels, par la formation des dimères, des thiones et des complexes de rhodium correspondants. Dans un second temps, ces nouveaux sels d'azolinium ont été évalués dans la réaction d'addition conjuguée de réactifs de Grignard sur des cétones α,β insaturées. Les résultats ont montré de très bonnes activités catalytiques, et de très bon
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Balanta, Castillo Angelica. "Novel molecular and colloidal catalysts for c-c bond formation processes." Doctoral thesis, Universitat Rovira i Virgili, 2011. http://hdl.handle.net/10803/66243.

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Esta tesis doctoral se centró en la síntesis y la caracterización de nanopartículas metálicas (Pd, Ni, Pt) estabilizadas por varios tipos de ligandos y el uso de estas nanopartículas en reacciones de formación de nuevos C-C o C-heteroatomo: a) Reacción de substitución alílica catalizadas por Pd; b) Reacción de acoplamiento asimétrico de Suzuki-Miyaura; c) Reacción de acoplamiento de Suzuki-Miyaura; d) reacción de adición 1,4 de ácidos borónicos a cetonas. En cada una de estas reacciones se llevó a cabo la síntesis y caracterización de nanoparticulas metálica y complejos moleculares usando muc
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Eichelsheim, Tanja. "Oligonucleotide based ligands in homogeneous transition metal catalysis." Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3168.

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Catalysis plays an important part in our society. Numerous transition metal catalysts have been developed which can convert many different substrates in a wide range of reactions. Catalysis also plays an important role in nature and therefore special catalysts, enzymes, have evolved over time. Enzymes are tremendously efficient giving high yields and selectivities both regio and chemical but have a limited substrate and reaction scope. It was speculated that by combining the two, an ideal catalyst can be obtained. We planned to achieve this by introducing a transition metal, the catalytic cent
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44

Posseme, Françoise. "Synthèse et évaluation biologique d'analogues borylés et fluorés de polyamines. Nouvelle voie d'accès stéréocontrôlée ayx (E)-(gamma-alocoxyallyl)boronates alpha-substutués." Rennes 1, 2001. http://www.theses.fr/2001REN10149.

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La première partie traite de la mise au point de nouveaux vecteurs d'atomes de bore 10 ou de fluor 18, en vue d'une utilisation en boroneurothérapie (BNCT) ou en tomographie par émission de positons (TEP). Dans un premier temps, un rappel bibliographique concernant les deux techniques met en évidence les exigences requises dans l'élaboration de telles molécules. En considérant les nombreuses propirétés polyamines, elles apparaissent comme des candidats potentiels, capables de vectoriser un hétéroélément dans un tissu cancéreux. Dans cette optique, nous avons synthétisé une série d'analogues de
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45

Hallman, Kristina. "Asymmetric Catalysis : Ligand Design and Conformational Studies." Doctoral thesis, KTH, Chemistry, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3275.

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<p>This thesis deals with the design of ligands for efficientasymmetric catalysis and studies of the conformation of theligands in the catalytically active complexes. All ligandsdeveloped contain chiral oxazoline heterocycles.</p><p>The conformations of hydroxy- and methoxy-substitutedpyridinooxazolines and bis(oxazolines) during Pd-catalysedallylic alkylations were investigated using crystallography,2D-NMR techniques and DFT calculations. A stabilising OH-Pdinteraction was discovered which might explain the differencein reactivity between the hydroxy- and methoxy-containingligands. The confor
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46

Newman, Louise M. "Asymmetric synthesis : approaches via enantiomerically pure acetal and oxazoline ligands." Thesis, Loughborough University, 1999. https://dspace.lboro.ac.uk/2134/13773.

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This thesis describes the synthesis of novel ligands that include enantiomerically pure acetal and oxazoline moieties. These ligands are utilised in a number of metalmediated asymmetric syntheses. All asymmetric acetals and pyridine based acetals are synthesised in good yield in a single step from their corresponding enantiomerically pure diols. C2 symmetric bisacetals are investigated as ligands in the organolithium and Grignard additions to benzaldehyde with promising results. C2 symmetric bisacetals and pyridine based acetals are tested for their ability to induce asymmetry in copper(l) cat
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47

Gillespie, Jason A. "Design and synthesis of wide bite angle phosphacyclic ligands." Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3100.

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By examining structure activity relationships for a given catalytic reaction it is possible to discover what ligand features and parameters lead to stable and highly active/selective catalyst systems. With this knowledge in hand it may be possible to rationally design next generation ligands and catalysts to affect improved substrate transformations, with higher selectivities and faster reaction times. The success of Burk's DuPhos ligands in asymmetric hydrogenation demonstrated that chiral phosphacycles can be a potent source of chiral induction, whilst in a similar vein the work of van Leeuw
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48

Chamseddine, Yssam. "Sondes mecanistiques chirales et/ou regioselectivement deuteriees : application a l'etude de quelques processus de substitution nucleophile." Paris 6, 1988. http://www.theses.fr/1988PA066133.

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49

Böhnisch, Torben. "C2-Symmetric Pyrazole-Bridged Ligands and Their Application in Asymmetric Transition-Metal Catalysis." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2015. http://hdl.handle.net/11858/00-1735-0000-0028-876A-6.

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50

Linstadt, Roscoe T. H. "A. Studies In The Allylic Substitution Chemistry Of Copper Hydride B. Stereoselective Silylcupration Of Conjugated Alkynes In Micellar Media C. Palladium-Catalyzed Synthesis Of 1,3-Butadienes and [3]-[6]Dendralenes D. Synthesis Of Small Molecule Underwater Adhesives Inspired By Mussels." Thesis, University of California, Santa Barbara, 2017. http://pqdtopen.proquest.com/#viewpdf?dispub=10257794.

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<p> Copper hydride (CuH) has been shown to enable a number of selective 1,2- and 1,4-reductions when complexed with the appropriate ligand, yet the allylic substitution chemistry of CuH has been much less studied. This dissertation describes the further study of CuH to perform sequential reductions on Morita-Baylis-Hillman (MBH) adducts. Specifically: I) Selectivity in the SN2&rsquo; reduction of MBH adducts was shown to be highly dependant on the nature of the ligand used. II) The reaction of MBH alcohols was shown to involve an initial dehydrogenative silylation with PMHS, where both the oli
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