Dissertations / Theses on the topic 'Allylic alcohols'
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Brennan, Meabh B. "Chemo- and stereoselective oxidation of allylic amino alcohols." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.531953.
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Hackett, Simon F. J. "Selective Oxidation of Allylic Alcohols on Palladium Catalysts." Thesis, University of York, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.490272.
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This thesis concerns the selective aerobic oxidation of allylic alcohols over practical and model palladium c~alysts. The goal was to elucidate the nature of the active catalyst site and origin of deactivation, which have hindered industrial implementation of such systems. It is hoped that understanding such fundamental aspects of the catalytic process will help optimise future· catalysts exhibiting high turnover frequencies as well as longer lifetimes on-stream. To realise these goals wet-chemical inorganic materials synthesis has been married with Ultra High Vacuum (UHV) single crystal methodologies. A series of amorphous, y-alumina supported palladium catalysts were prepared containing variable Pd concentrations. These allowed the impact of particle size on their resultant catalysis to be studied systematically. Characterising these small metal particles proved challenging, necessitating the combination of powerful bulk and surface sensitive techniques including X-ray Absorption (XAS) and Xray Photoelectron Spectroscopy (XPS) to identify the nature/structure ofthe active phase. These measurements revealed a progressive transformation from large metallic Pd clusters to small oxidised palladium clusters with decreasing precious metal loading. The concentration of surface palladium oxide correlated with the Turnover Frequency (TOF) towards the selective oxidation of both crotyl and cinnamyl alcohols. Surfactant templating routes were subsequently employed to produce high . surface, area mesoporous alumina supports, with a view to boosting the palladium dispersion and proportion of active metal oxide. Bulk and surface spectroscopies revealed similar trends in Pd cluster size and oxidation state with loading as observed for the amorphous supports, albeit with smaller more heavily oxidised palladium at the lowest loadings. High-resolution, high angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) revealed that mesoporous alumina was able to stabilize isolated Pd(II) atoms on its surface. Synergy between these atomically-dispersed reduced palladium centers, and improved reactant/product mass transport through the mesoporous structure resulted in extremely active catalysts for alcohol selective oxidation. Decreasing II' II J _ _~ ~ t. ', ...... '... - - - ....:-. .• the Pd concentration increased TOFs as observed for the amorphous alumina catalysts. The single-site catalyst possessed initial TOFs of4400 and 7080 hr-I for cinnamyl and crotyl alcohol oxidation to their respective aldehydes. In order to shed insight into/the un~erlying reactant/surface interaction and deactivation mechanism, UHV studies were subsequently conducted over Pd(lll) single crystal surfaces, to model the most stable (111) facets of larger metal clusters found in practical oxidation catalysts. The adsorption geometry and thermal chemistry of both benzene and bromobenzene were first studied to examine the interaction of the phenyl group in cinnamyl alcohol with Pt(111). Fast XPS and NEXAFS spectra shoW that both benzene and bromobenzene adsorb non-dissociatively, but whilst the former bonds parallel to the surface, bromobenzene shows a significant tilt angle of-60°. Thermal-desorption spectroscopy showed that 20 % of a saturated benzene monolayer desorbs intact in two states, with the remainder undergoing successive dehydrogenations depositing surface-bound hydrocarbon fragments. For bromobenzene, low temperature C-Br bond cleavage results in surface-bound -phenyl groups. A proportion ofthese dehydrogenate at 400 K, liberating hydrogen which subsequently reacts with bromine, or other surface bound phenyls, yielding HBr, benzene and H2. Approximately 30% of a bromobenzene monolayer desorbs either reversibly or as reactively-formed hydrocarbons. The chemistry of crotyl alcohol was subsequently explored on clean and oxygen covered Pd (111) surfaces. Synchrotron X-ray experiments were 'combined with laboratory mass spectrometry to elucidate the associated binding geometry and reaction network. NEXAFS and Fast XPS revealed crotyl alcohol adsorbs molecularly at 95 K, with the allyl moiety parallel to the surface. Surface_ annealing induces oxidative dehydrogenation to crotonaldehyde at sub-ambient temperatures, in competition with a minor dehydration route to butene and water. Crucially, alcohol decarbonylation was also observed at catalytically relevant temperatures, resulting in an accumulation of surface bound CO and hydrocarbon fragments over the bare metal surface. Coadsorbed oxygen suppressed this decarbonylation pathway, promoting crotonaldehyde desorption over a similar temperature regime to that observed over dispersed PdfAh03 clusters.
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Gao, Y. (Yun). "Synthesis and synthetic transformations of allylic alcohols, epoxy alcohols, and 1,2-cyclic sulfates." Thesis, Massachusetts Institute of Technology, 1988. http://hdl.handle.net/1721.1/14588.
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Khan, Afzal. "Synthesis and reactions of epoxides." Thesis, University of Sheffield, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.286509.
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Peters, Byron. "Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-122419.
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The work described in this thesis is focused on exploring the efficacy of asymmetric iridium catalysis in the hydrogenation of challenging substrates, including precursors to chiral sulfones and chiral cyclohexanes. Furthermore, iridium catalysis was used to isomerise allylic alcohols to aldehydes, and in a formal total synthesis of Aliskiren (a renin inhibitor). A large variety of unsaturated sulfones (cyclic, acyclic, vinylic, allylic and homoallylic) were prepared and screened in the iridium catalysed hydrogenation reaction using a series of previously developed N,P-ligated Ir-catalysts. The outcome was a highly enantioselective (>90% ee) protocol to prepare sulfones bearing chiral carbon scaffolds, sometimes having purely aliphatic substituents at the stereogenic centre. Furthermore, performing the Ramberg-Bäcklund reaction on the chiral products, under optimised conditions, produced cyclic and acyclic unsaturated derivatives without erosion of enantiomeric excess. This hydrogenation protocol was also successful in the hydrogenation of a number of cyclohexene-containing compounds. Minimally functionalised, functionalised and heterocycle-containing cyclohexenes were hydrogenated in up to 99% ee. Hitherto, both chiral sulfones and chiral cyclohexanes have been challenging targets for most catalytic asymmetric methodologies. Although the preparation of aldehydes and ketones by isomerisation of the corresponding allylic alcohol is well established, there has been limited success in the development of good enantioselective protocols. For the isomerisation of a number γ,γ-allylic alcohols to the corresponding chiral aldehydes, high enantioselectivities (up to >99% ee) and modest yields were achieved using an N,P-iridium catalyst. Noteworthy is the high selectivity obtained for isomerisation of Z and dialkyl γ,γ-allylic alcohols, which prior to this study had been difficult to isomerise in high enantioselectivity. Preparation of a key intermediate used in the synthesis of Aliskiren, a renin inhibitor drug was also accomplished. Using a convergent synthesis strategy, two allylic alcohol fragments were hydrogenated with high enantiomeric excess (>92% ee). These fragments were then joined using a Julia-Kocienski reaction, providing >95% E geometry around the C=C bond, which was crucial for the subsequent steps in the synthesis.At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.
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Smith, Torben J. N. "Enantioselective deprotonations of three membered rings." Thesis, University of Nottingham, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243768.
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Lee, Wai-Man. "Stereocontrolled synthesis of polysubstituted tetrahydropyrans and #delta#-lactones via tandem [2,3]-Wittig-anionic oxy-Cope rearrangement." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243034.
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Evans, Paul. "The epoxy Ramberg Bäcklund rearrangement (ERBR) and related studies." Thesis, University of York, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.265373.
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Otoo, Barnabas. "Conjugate Additions and Transposition of the Allylic Alcohols of Enol Ethers of 1, 2-Cyclohexanedione." Digital Commons @ East Tennessee State University, 2010. https://dc.etsu.edu/etd/1748.
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A variety of protected enolic forms of 1, 2-cyclohexanedione was prepared as substrates for conjugate addition studies using organocopper reagents. The sequence involved the enol ether preparation via the enolate, alkylation with an organometalic reagent, and oxidative rearrangement with pyridinium chlorochromate followed by the conjugate addition reactions. Protection of 1, 2-cyclohexanedione was achieved by reacting with chloro tert-butyldimethyl silane and subjected to alkylation. Steric problems were encountered and so an alternative protective group the methoxymethyl acetal was prepared and studied. Alkylation of these derivatives was successful; however, the oxidation was problematic and although evidence for rearrangement was observed in one case, it did not provide the desired ketone.
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Qiu, Shuai. "Trifluoromethoxylation of Allylic Alcohols via 1,2-Aryl Migration Promoted by Visible Light-Mediated Photoredox Catalysis." Thesis, KTH, Skolan för kemi, bioteknologi och hälsa (CBH), 2020. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-278836.
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Visible light photoredox catalysis has proven to be a powerful tool for promoting transformations in organic synthesis. Hence this project was carried out to develop tools for predicting reactivity patterns of visible light- promoted redox reactions. Fluorination is of immense importance in organic chemistry, and so is trifluoromethoxylation. The fluorination reaction has been studied for a long time and has been accomplished in milder ways, while the generation of a trifluoromethoxy-radical at room temperature and atmospheric pressure remains a challenge. The design of the reaction in this project is to overcome the instability and take control of the catalytic event under visible- light photocatalytic conditions. The trifluoromethoxylation reaction proceeded at room temperature with the reaction time of 60 min using acetonitrile as the solvent and blue LED (10 W) as the external light source. No yield of the desired product was obtained for any of the substrates. More surprisingly, in all entries, 3,3-diphenylprop-2-en-1-ol was attained as a side product. The same side product was also detected in the entry with ambient light, concluding that the reaction was completed without any external light source. Thus, no photoredox catalysis took place.Fotoredoxkatalys via ljus inom det synliga spektrat har visat sig vara ett kraftfullt verktyg för att gynna reaktioner inom organisk syntes. Detta projekt genomfördes med syfte att utveckla verktyg avsedda för att förutspå reaktivitetsmönster vid fotoredoxkatalys med synligt ljus. Fluorinering och trifluorometoxylering är viktiga verktyg inom organisk syntes. Fluorineringsreaktionen har studerats länge och har kunnat genomföras under milda reaktionsbetingelser, medan generering av trifluorometoxyradikal vid rumstemperatur och atomsfärstryck fortfarande är en utmaning. Reaktionen i det här projektet är designad för att kringgå instabilitetsproblemet och ta kontroll över katalysmomentet, under fotokatalysförhållanden i synligt ljus. Reaktionen utfördes i rumstemperatur med en reaktionstid på 60 minuter, med acetonitril som lösningsmedel och blå LED (10 W) som extern ljuskälla. Inget av substraten reagerade till den önskade produkten. Mer överraskande var att 3,3-difenylprop-2-en-1-ol erhölls som sidoprodukt vid alla reaktionsstillfällen. Samma sidoprodukt upptäcktes även vid reaktion genomförd i dagsljus, vilket indikerar att reaktionen skedde utan någon extern ljuskälla. Således skedde ingen fotoredoxkatalys.
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Love, Christopher J. "The carbometallation of allylic alcohols : scope stereochemistry, and a synthesis of a precursor to Tsukubaenolide (FK 506)." Thesis, University of Southampton, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.303109.
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Liu, Jianguo. "Iridium Catalysed Asymmetric Hydrogenation of Olefins and Dynamic Kinetic Resolution in the Asymmetric Hydrogenation of Allylic Alcohols." Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-140923.
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The work described in this thesis is focused on exploring the efficacy of iridium-catalysed asymmetric hydrogenation of precursors to chiral alcohols and chiral cyclohexanes. A range of allylic alcohols including γ,γ-dialkyl allylic alcohols and (Z)-allylic alcohols were prepared and evaluated in the asymmetric hydrogenation using iridium catalysts resulting in chiral alcohols in high yields and excellent enantioselectivity. This methodology was applied in the formal synthesis of Aliskiren, an efficient renin inhibitor drug, using the asymmetric hydrogenation of an allylic alcohol as a key-step. Another project concerned the dynamic kinetic resolution of racemic secondary allylic alcohols using Ir-N,P catalysts under hydrogenation conditions. A range of secondary allylic alcohols and protected alcohols were evaluated in the asymmetric hydrogenation via dynamic kinetic resolution using Ir-N,P catalysts. The corresponding chiral saturated alcohols were formed in good yield with excellent diastereoselectivites (up to 95/5) and enantioselectivities (>99% ee). The last part of this thesis is directed towards the development of highly regio- and enantioselective asymmetric hydrogenation of 1,4-cyclohexadienes and its application in the preparation of useful chiral cyclohexenone intermediates. Non-functionalised, functionalised and heterocycle-containing cyclohexadienes were evaluated. Good yield of regioselectively mono-hydrogenated silyl protected enol ethers were obtained in most cases with excellent enantioselectivity.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 5: Manuscript.
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Dai, Xiaoyang. "Hydride transfer reactions of trifluoromethylated allylic alcohols and ketimines & nucleophilic trifluoromethylthiolation of Morita-Baylis-Hillman Carbonates." Thesis, Rouen, INSA, 2014. http://www.theses.fr/2014ISAM0018/document.
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Nous avons développé de nouveaux accès pour la construction de molécules comportant les motifs Csp3-CF3 et Csp3-SCF3. Deux réactions de transfert d'hydrure sur des composés trifluorométhylés par catalyse avec des métaux de transition ont été réalisées : 1) l'isomérisation catalytique d'alcools allyliques trifluorométhylés par des complexes de fer (II); 2) le transfert d'hydrogéne énantiosélectif de céto-imines trifluorométhylées par des complexes chiraux de ruthénium en utilisant l'isopropanol comme source d'hydrure pour obtenir des amines trifluorométhylées optiquement actives avec de hauts rendements et de hautes énantiosélectivités. La trifluorométhylthiolation allylique nucléophile de dérivés de Morita-Baylis-Hillman a été étudiée. L'accès régio- et stéréosélectif aux produits SCF3 thermodynamiques a été réalisé par la combinaison de S8/CF3SiMe3/KF/DMF avec de bons rendements. Le produit cinétique a été obtenu en utilisant le réactif de ZardWe have developed new accesses for the construction of molecules featuring Csp3-CF3 and Csp3-SCF3 motifs. Two atom-economical hydride transfer reactions of trifluoromethylated compounds by transition-metal catalysis were realized: 1) the isomerization of trifluoromethylated allylic alcohols by iron (II) complexes; 2) the enantioselective transfer hydrogenation of trifluoromethylated ketimines by a chiral complex of ruthenium and isopropanol as hydride source for the preparation of optically pure trifluoromethylated amines in high yields and high enantioselectivities. The nucleophilic allylic trifluoromethylthiolation of Morita-Baylis-Hillman derivatives was investigated. The regio- and stereoselective access to thermodynamic trifluoromethylthiolated products has been achieved by combination of S8/KFfMe3SiCF3/DMF in good yields. The kinetic trifluoromethylthiolated products were obtained by using Zard's trifluoromethylthiolating reagent
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Thalén, Lisa K. "Transition metal- and enzyme-catalyzed reactions of primary amines and allylic alcohols : powerful tools in the preparation of pharmaceutically important compounds /." Stockholm : Department of Organic Chemistry, Stockholm University, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-38839.
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Diss. (sammanfattning) Stockholm : Stockholms universitet, 2010.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript. Paper 7: Manuscript. Härtill 7 uppsatser.
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Gadamsetty, Surendra Babu. "Application of sulfonimidoyl substituted allyltitanium (IV) complexes to the asymmetric synthesis of alkenyloxiranes, 2,3-dihydrofurans, tetrahydrofurans, unsaturated proline analogues and allylic alcohols." [S.l.] : [s.n.], 2007. http://deposit.ddb.de/cgi-bin/dokserv?idn=983701350.
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祐士, 中村, and Yushi Nakamura. "原子効率に優れたアリルアルコール類の新規触媒的分子変換法に関する研究." Thesis, https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13045024/?lang=0, 2017. https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB13045024/?lang=0.
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遷移金属錯体を触媒とした原子効率に優れたアリルアルコール類の新規変換法の開発について検討した。アリルアルコール類のアルコールとしての性質に着目し、主に"Borrowing hydrogen"方法論に基づいた反応開発について検討した結果, 独自に調製された高度な水素移動制御を可能とするルテニウム触媒を用いることで、原子効率100%のアリルアルコール類のanti-Markovnikov型ヒドロアミノ化反応やヒドロアルコキシ化を始めとした反応の開発に成功した。Development of novel transform methods of allylic alcohols catalyzed by transition metal complexes was studied. In the result, development of anti-Markovnikov hydroamination and hydroalkoxylation of allylic alcohols catalyzed by uniquely prepared ruthenium catalysts, which had a advanced transfer hydrogen ability, on the basis of a character as a alcohol of allylic alcohols and "Borrowing hydrogen" methodology was achieved at 100% atom economy.
博士(工学)
Doctor of Philosophy in Engineering
同志社大学
Doshisha University
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Bunge, Alexander. "Geminale Dihydroperoxide als Sauerstofftransferreagenzien und Synthesebausteine." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2011. http://dx.doi.org/10.18452/16436.
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Im Rahmen dieser Dissertation wurden die Herstellung sowie Reaktionen von geminalen Dihydroperoxiden erforscht. Dabei kamen die dargestellten Dihydroperoxide sowohl als Sauerstofftransferreagenz, insbesondere zur enantioselektiven Epoxidation, als auch als Baustein zur Synthese von 1,2,4,5-Tetroxanen zum Einsatz. Es wurde eine in unserem Arbeitskreis gefundene Methode zur Darstellung gem - Dihydroperoxide zunächst hinsichtlich der Reaktionsbedingungen optimiert, um dann eine Vielzahl an Dihydroperoxiden vornehmlich mit dieser Methode zu synthetisieren. Insbesondere gelang es hier erstmals, primäre Dihydroperoxide aus aliphatischen Aldehyden darzustellen. Desweiteren wurde erstmals eine größere Anzahl an enantiomerenreinen DHPs dargestellt. Weitere DHPs konnten durch Ozonolyse von olefinischen Terpenen mit etherischer Wasserstoffperoxidlösung dargestellt werden. Die enantiomerenreinen DHPs wurden verwendet, um enantioselektiv sowohl 2-substituierte Naphthochinone wie auch Allylalkohole, insbesondere tertiäre Allylalkohole, zu epoxidieren. Die Epoxide der letzteren sind nach der normalerweise verwendeten Methode nach Sharpless nicht zugänglich. Außerdem konnten durch Sulfidoxidation Sulfoxide enantiomerenangereichert dargestellt werden. Dies stellt die erste Nutzung von geminalen Dihydroperoxiden zur enantioselektiven Sauerstoffübertragung dar. Die primären aliphatischen gem-DHPs wurden desweiteren zur Darstellung bisher unbekannter 1,2,4,5-Tetroxane genutzt. Insbesondere wurde gefunden, daß durch Kondensation mit Orthoestern verläßlich alkoxysubstituierte Tetroxane erzeugt werden können. Diese wurden in der Literatur bisher nur an sehr wenigen Beispielen beschrieben.In the course of this dissertation thesis the preparation and reactions of geminal dihydroperoxides were researched. The hereby synthesized dihydroperoxides were used as an oxygen transfer reagent, especially for enantioselective epoxidation, as well as a building block for the synthesis of 1,2,4,5-tetroxanes. A method for synthesis of gem-dihydroperoxides that was found in our workgroup was first optimized concerning reaction conditions, and later utilized to synthesize a large number of dihydroperoxides. It was notably possible to synthesize primary DHPs from aliphatic aldehydes for the first time. Also for the first time, a large number of enantiomerically pure gem-DHP was prepared by this method. Additional enantiomerically pure DHPs were made by ozonolysis of olefinic terpenes using ethereal hydrogen peroxide solution. The enenantiomerically pure DHPs were utilized to both epoxidize 2-substituted naphthoquinones as well as allylic alcohols, especially tertiary allylic alcohols. The latter kind does not react via the normally used Sharpless epoxidation. Additionally, enantioenriched sulfoxides could be prepared from sulfides. This is the first time that geminal dihydroperoxides were used for enantioselective oxygen transfer. Primary aliphatic DHPs were further utilized to prepare previously unknown 1,2,4,5-tetroxanes. Notably it was found that condensation with orthoesters reliably yielded alkoxy-substiuted tetroxanes. These were only described in a very few cases in literature before.
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Gerez, Thierry. "Développement de catalyseurs pour le transfert d'hydrogène : application à des molécules biosourcées." Thesis, Lyon 1, 2014. http://www.theses.fr/2014LYO10246/document.
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Dans la présente étude, la compatibilité de molécules polyfonctionnelles a été évaluée en oxydation catalytique aérobie. L'oxydation du géraniol en citral a été réalisée dans un mélange t-BuOH/eau à 40°C en présence de Pt/C et Pt-Bi/C. A 90°C, l'oxydation sélective du 8-Chloro-1-Octanol en acide 8-Chlorooctanoïque a été réalisée. Par contre, d'autres substrats n'ont pas pu être transformés sélectivement en aldéhyde ou en acide à cause de leur sensibilité vis-À-Vis de l'oxygène (alcool-A) ou de leur réactivité particulière (5-Chloro-1-Pentanol qui est cyclisé en produits non désirés). En conditions anaérobies, le transfert d'H alcool / accepteur a été développé, à partir du géraniol (alcool allylique) comme substrat modèle : il convient de réaliser soit la déshydrogénation sélective de sa fonction alcool, soit son isomérisation lorsque la fonction alcool est déshydrogénée en même temps que la C=C allylique est hydrogénée. Les catalyseurs au Cu supporté ont montré un potentiel beaucoup plus prometteur que les métaux nobles, et de nombreux supports ont été évalués. Le styrène utilisé comme accepteur d'H ne permet pas d'obtenir sélectivement le produit de déshydrogénation du géraniol (citral), par contre l'utilisation d'un accepteur d'H confidentiel permet d'obtenir sélectivement le citral sans former de citronellal (produit d'isomérisation de la fonction alcool allylique) en présence de catalyseur au cuivre sur un support ex-Hydrotalcite. En l'absence d'accepteur, ce catalyseur permet l'isomérisation sélective de différents alcools allyliques avec des sélectivités jusqu'à 90 % en cétones saturéesIn this study, we evaluated the compatibility of polyfunctional alcohols with catalytic aerobic oxidation systems. Geraniol dehydrogenation was carried out in mild conditions (t-BuOH / water mixture as solvent, 40°C) in the presence of Pt / C (promoted with Bi to avoid leaching). These catalysts are efficients for the oxidation of 8-Chloro-1-Octanol into corresponding acid at 90°C. However, other reactants were not selectively transformed into aldehyds or acids because of their oxygen sensivity (alcool-A) or their particular reactivity toward cyclization products (5-Chloro-1-Pentanol). In parallel, H transfer dehydrogenation was developed in anaerobic conditions. Geraniol was choosen as a model molecule since it can be selectively dehydrogenated or isomerizd (a reducible function on the substrate is hydrogenated when alcohol function is dehydrogenated). Some noble metals were evaluated for these reactions (Pd in the presence of alkene as H acceptor or Ag for acceptorless dehydrogenation), but performances and selectivities are quite low. Copper catalysts showed better results, and a lot of supports were evaluated. Selectivity toward dehydrogenation product (citral) is not total when styrene is used as hydrogen acceptor, but the use of another H acceptor (confidential) in the presence of copper supported on modified hydrotalcite catalyst allows selective dehydrogenation of geraniol without isomerization intro citronellal. Without H acceptor, this catalyst leads to selective isomerization of secondary allylic alcohols into saturated ketones (90 % selectivity)
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Kasprzyk, Milena, and milena kasprzyk@freehills com. "Synthetic Studies Towards the Tridachione Family of Marine Natural Products." Flinders University. Chemistry, Physics and Earth Sciences, 2008. http://catalogue.flinders.edu.au./local/adt/public/adt-SFU20081107.085933.
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Since the middle of the 20th century, significant interest has evolved from the scientific community towards the polypropionate family of marine natural products. A number of these compounds have been shown to possess significant biological activity, and this property, as well as their structural complexity, has driven numerous efforts towards their synthesis. The first chapter provides an introduction into the world of polypropionates, with a discussion on synthetic studies into a number of members of the tridachiapyrone family. Fundamental synthetic concepts utilised in this thesis towards the preparation of polyketides are also described, with a focus on their application towards the synthesis of 9,10-deoxytridachione, anti tridachiahydropyrone and syn tridachiahydropyrone.
Chapter 2 describes the work undertaken towards the total synthesis of 9,10-deoxytridachione. The novel tandem conjugate addition-Dieckmann condensation of complex enones developed previously in the Perkins group was used to generate anti methylated cyclohexenones as key synthetic intermediates. The conversion of the cyclohexenones into the corresponding cyclohexadienes via allylic alcohols was attempted, utilising a Grignard-mediated reaction to achieve the selective 1,2-reduction. Studies into the Grignard-mediated reduction were also undertaken on seven additional cyclohexenones, in order to investigate the utility and scope of the reaction.
The extension of the methodology previously developed for the synthesis of cyclohexenones is the subject of Chapter 3. This section describes investigations into the synthesis of stereochemically-diverse cyclohexenones from complex enones. The conjugate addition-Dieckmann condensation strategy was extended successfully towards the synthesis of a syn methylated cyclohexenone, which allowed the synthesis of the proposed true structure of tridachiahydropyrone to be pursued.
The methodology developed in Chapter 3 was utilised in Chapter 4 to synthesise a model system of syn tridachiahydropyrone. A comparative analysis of the NMR data of the syn model, an anti model and anti tridachiahydropyrone with the natural product indicated that the true structure of tridachiahydropyrone may indeed have syn stereochemistry. The synthesis of syn tridachiahydropyrone was attempted, and to this end a suitable cyclohexanone was successfully synthesised. However, the subsequent methylation-elimination cascade failed to furnish the desired syn methylated cyclohexenone, producing only an anti methylated cyclohexanone. The stereochemistry of the methylation was deduced using high and low variable temperature NMR coupled with selective irradiation NOESY.
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Schäfer, Christian. "Reactivity of acetylenic ω-keto-esters towards transition metal complexes : synthesis of polycyclic motives of natural products." Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF006/document.
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Les travaux décrits dans ce mémoire ont pour objet l’étude de la réactivité des ω-céto-esters acétyléniques vis-à-vis des métaux de transition. Lorsque ces composés sont traités avec une mélange Ti(OiPr)4/iPrMgBr, la formation d’alcools allyliques bicycliques est observée avec une totale diastéréosélectivité par rapport à la jonction de cycle (cis) et une configuration (E) pour la double liaison. Il a été montré que ces produits peuvent être transformés en lactone α,β-insaturé, sous-structures de produits naturels. La cycloisomérisation d’alcynyl cétones catalysées par des sels d’Ag(I) conduit à la formation de composés spiraniques. En piégeant l’intermédiaire réactionnel, la synthèse des composés vinyl-iodés correspondants a été réalisée. Si la réaction de cycloisomérisation est effectuée avec des ω-céto-esters acétyléniques, des ester α,β-insaturés sont isolés. Les produits obtenus ont ensuite été utilisés comme substrats pour la formation de systèmes tricycliques 6-5-5 et 6-6-5. Ces enchaînements de cycles sont présents dans le squelette carboné d’une grande variété de produits naturels. Les travaux décrits dans ce mémoire ont pour objet l’étude de la réactivité des ω-céto-esters acétyléniques vis-à-vis des métaux de transition. Lorsque ces composés sont traités avec une mélange Ti(OiPr)4/iPrMgBr, la formation d’alcools allyliques bicycliques est observée avec une totale diastéréosélectivité par rapport à la jonction de cycle (cis) et une configuration (E) pour la double liaison. Il a été montré que ces produits peuvent être transformés en lactone α,β-insaturé, sous-structures de produits naturels. La cycloisomérisation d’alcynyl cétones catalysées par des sels d’Ag(I) conduit à la formation de composés spiraniques. En piégeant l’intermédiaire réactionnel, la synthèse des composés vinyl-iodés correspondants a été réalisée. Si la réaction de cycloisomérisation est effectuée avec des ω-céto-esters acétyléniques, des ester α,β-insaturés sont isolés. Les produits obtenus ont ensuite été utilisés comme substrats pour la formation de systèmes tricycliques 6-5-5 et 6-6-5. Ces enchaînements de cycles sont présents dans le squelette carboné d’une grande variété de produits naturelsIn this work, the reactivity of acetylenic ω-ketoesters towards different metal complexes was investigated. When acetylenic ω-ketoesters are submitted to Ti(OiPr)4/iPrMgBr, the formation of fused bicyclic γ-hydroxy-α,β-unsaturated esters was observed. The products were obtained with absolute selectivity in regard to the ring junction formed (cis) and the configuration of the double bond (E) and could be transformed into the corresponding α,β-unsaturated lactones, substructures of various natural products. When ω-ketoalkynes are used in Ag(I)-catalyzed cycloisomerization reactions, the formation of spirocyclic compounds was observed. By taking advantage of the reaction intermediates of this reaction, it was possible to isolate the corresponding spirocyclic alkenyl iodides. Performing cycloisomerization reactions with acetylenic ω-ketoesters, spirocyclic α,β-unsaturated esters are formed. We could show that these products are valuable substrates for the formation of 6-5-5- and 6-6-5-fused tricyclic systems which represent the skeleton of a large group of natural products
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Black, Phillip James. "Catalytic electronic activation : the addition of nucleophiles to an allylic alcohol." Thesis, University of Bath, 2002. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.275782.
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Fordred, Paul. "Synthetically useful alkene isomerisation and hydroboration reactions." Thesis, University of Bath, 2012. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.558880.
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Upon treatment with a palladium catalyst and hydrogen gas in the presence of caesium carbonate, a wide range of exomethylenic allylic alcohols were found to afford their corresponding trisubstituted isomers. Although hydrogenation was an unavoidable competing pathway, careful monitoring of the reaction progress allowed the desired isomerised products to be obtained in moderate to excellent yields and high (E):(Z) ratios.
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Morrison, Ryan John. "Development and Application of Methods for Enantioselective Synthesis of Amines and Alcohols:." Thesis, Boston College, 2020. http://hdl.handle.net/2345/bc-ir:108988.
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Thesis advisor: Amir H. HoveydaHomoallylic amines and alcohols, particularly those amenable to further functionalization, are among the most widely used building blocks in chemical synthesis and are typically accessed by addition of an allyl-metal compound to an electrophile. Studies discussed herein have focused on advancing stereoselective synthesis of versatile allylboron compounds and their utilization in catalytic regio-, diastereo-, and enantioselective addition to various electrophiles. Mechanistic principles have been central to the investigations described in this thesis, and it has been on this basis that catalytic strategies for practical synthesis of bioactive molecules were developed. Chapter One. Vicinal amino alcohols are ubiquitous in natural products and serve as versatile synthetic intermediates and we envisaged that diastereo- and enantioselective additions of O-substituted allyl boronates offers an attractive option to access these motifs. In the presence of zinc (II) methoxide as co-catalyst, it will be demonstrated that sequence of events may occur, wherein isomerization of an initially formed allyl complex occurs prior to addition of an aldimine with kinetic selectivity. As will be described, through the use of an optimal catalyst, N-protecting/activating group and appropriate reaction conditions, differentially protected vicinal amino alcohol derivatives may be synthesized in high enantiopurity. The utility of the approach is highlighted through synthesis of an NK1 agonist. Chapter Two. It will be demonstrated that additions of various organoboron compounds converts readily accessible and easy-to-handle silyl-substituted -tertiary amines. Contrary to additions to aldimines, isomerization of the initially generated aminophenol-allyl complex is preempted, suchthat linear products are favored. DFT analysis suggests that high enantioselectivity likely originates from attractive electrostatic interaction between a trifluoromethyl group and the catalyst’s ammonium moiety. The synthetic utility was highlighted through concise, enantioselective synthesis of a key intermediate of a recently reported BACE-1 inhibitor on gram scale. Chapter Three. This section details the development of a method for direct synthesis of homoallylic alcohols bearing a Z-alkenyl chloride, which may be directly subjected to stereo-retentive cross coupling without wasteful protection/deprotection or redox operations. Products were obtained in high regio- and enantioselectivity for aliphatic, alkenyl- and heteroaryl-substituted aldehydes. The approach was utilized in a concise, protecting group-free synthesis of anti-tumor agent mycothiazole. Chapter Four. A method for stereoselective synthesis of fluorine-containing trisubstituted allyl boronates will be presented. It will then be illustrated that in the presence of an appropriate aminophenol catalyst, a large assortment of homoallylic alcohols containing a quaternary fluoro- and trifluoromethyl-substituted stereogenic center may be obtained with efficiency and high diastereo- and enantioselectivity. The obtained products were then elaborated to the furanose core of Sofosbuvir, a recently approved treatment for hepatitis C
Thesis (PhD) — Boston College, 2020
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
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El, Karroumi Jamal. "Réactions de carbonylation de substrats naturels de plantes." Thesis, Toulouse, INPT, 2014. http://www.theses.fr/2014INPT0033/document.
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La fonctionnalisation par voie catalytique de substrats naturels a été menée dans le but d’accroître l’activité biologique reconnue de la molécule naturelle de départ ou de découvrir de nouvelles activités. Des réactions catalytiques telles que l’hydroformylation et l’alcoxycarbonylation mettant en jeu le monoxyde de carbone et catalysées par des complexes du rhodium et du palladium ou encore la réaction de cycloisomérisation catalysée par des complexes d’or ou du platine ont déjà permis d’accéder sélectivement à de nouvelles molécules intéressantes. Dans une première partie nous nous sommes intéressés à l’huile essentielle du cèdre de l’atlas (cedrus atlantica) qui est constituée d’une partie hydrocarbure et d’une partie oxygénée. Notre étude s’est focalisée sur la partie oxygénée de l’huile essentielle du cèdre de l’atlas qui est composée de deux cétones isomères, les Z- et E-α- atlantones. La réaction de cyclocarbonylation des alcools allyliques dérivés des α-atlantones a été étudiée. Cette réaction catalysée par des complexes du palladium permet d’obtenir des lactones à 5 et à 6 chainons. Plusieurs systèmes catalytiques de type [PdCl2L2]/SnCl2.2H2O ont été testés, lors de cette étude et nous avons montré que la regiosélectivité de la réaction peut être contrôlée par la nature du ligand utilisé. Ainsi, les ligands monophosphines favorisent la formation des lactones à 6 chainons obtenues sous forme de deux diastéréoisomères et les ligands diphosphines favorisent la formation de celles à 5 chainons obtenues sous forme de quatre diastéréoisomères. Ces lactones sont complètement caractérisées par RMN 1D et 2D et la spectrométrie de masse. Des monocristaux ont été obtenus et analysés par diffraction des rayons X. Dans une deuxième partie, la synthèse d’aldéhydes par réaction d’hydroformylation à partir de l’estragol, un allylbenzène extrait de l’huile essentielle de l’estragon, a été étudiée en présence du système catalytique [Rh(cod)(OMe)]2/ligand phosphole. Ainsi, nous avons évalué l’activité de plusieurs ligands phospholes dans cette réaction d’hydroformylation. Tous les ligands phospholes testés se sont révélés actifs et chimiosélectifs dans la réaction d’hydroformylation d’estragol pour donner majoritairement l’aldéhyde linéaire correspondant. Dans une étude préliminaire, nous avons étudié la réaction de cycloisomérisation d’énynes oxygénés dérivés d’α-atlantones catalysée par des complexes d’or ou du platineThe catalytic functionnalisation of the natural substrates have been developped to increase their own biological activity or to give them new biological properties. The reactions such as hydroformylation, alkoxycarbonylation and cyclocarbonylation in presence of carbon monoxide catalyzed by rhodium or palladium complexes or cycloisomerisation catalyzed by gold or platinium complexes give an access to new interesting molecules with high selectivity. In first part we have been interested in study of the essential oil of the Atlas Cedar (Cedrus Atlantica). We focused in this study on the oxygenated fraction, which contains the two sesquiterpenic ketone,isomers Z- and E-α-atlantone. Starting from allylic alcohols derived from α-atlantone, the cyclocarbonylation reaction catalyzed by palladium complexes have been investigated. This reaction provide a mixture of five and six membered ring lactones with excellent conversion and excellent chemioselectivity. Different catalytic systems [PdCl2L2]/SnCl2.2H2O or [Pd(OAc)2]/L have been studied. The regiochemical control depends on the nature of the ligand L. The monophosphine ligands favor the formation of the six-membered ring lactones obtained as two diastereomers, while the diphosphine ligands allow the formation of the five- membered ring lactone obtained as four diastereomers. These new lactones were fully characterized by 1D and 2D NMR and mass spectrometry. Monocrystals of the six- and five-membered ring lactones suitable for X-ray diffraction analysis have been obtained. In a second part the hydroformylation reaction of estragol, a natural allylbenzene extracted from the essential oil of estragon, have been studied with the catalytic system [Rh(cod)(OMe)]2/phospholes. All the phosphole ligands show good activities and chemoselectivities in the hydroformylation of estragol and affords the linear aldehyde corresponding as a major product. In a preliminary study, we have investigated the cycloisomerisation reaction of o-tethered enynes derived from α-atlantones catalyzed by gold or platinum complexes
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Al, Badri Hashim. "Synthèse et réactivité d'énamines phosphoniques fonctionnelles et de phosphonates allyliques. Applications à la synthèse de diènes fonctionnels utilisés dans la réaction de Diels-Alder." Rouen, 1996. http://www.theses.fr/1996ROUES054.
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Dans ce travail, de nouvelles applications des énamines phosphoniques et des phosphonates allyliques fonctionnels ou non ont été étudiées. La première partie du travail concerne l'étude de la réactivité des énamines 2-phosphoniques 2-fonctionnelles N, N'-diméthylées vis-à-vis de différents nucléophiles. Cette étude a permis l'accès à des phosphonates allyliques 2-fonctionnels qui ont été utilisés dans la synthèse de nouveaux butadiènes 2-carboxylates diversement substitués. Par ailleurs une voie d'accès particulièrement simple aux énamines 2-phosphoniques 2-fonctionnelles N-arylées a été mise au point. La deuxième partie de ce mémoire s'intéresse à la synthèse de différents phosphonates insaturés fonctionnels. La réaction des carbanions issus des phosphonates allyliques non fonctionnels vis-à-vis de différents électrophiles conduit à des nouveaux phosphonobutadiènes diversements substitués, à des (1-E)-2-phosphonobutadiénols ou à des diénoxyphosphonates acétylés et silylés ainsi qu'à des phosphonates allyliques 2-silylés. La réaction des carbanions des phosphonates allyliques 2-silylés permet également l'accès à d'autres types de composés organophosphorés intéressants, en particulier à des phosphonates 2, 3-insaturés 3-fonctionnels aptes à subir des transformations chimiques ultérieures par exemple dans la chimie des rétinoïdes, ainsi que des butadiènes phosphoniques, des phosphonolactones et des alkoxydiènes phosphoniques. Enfin, les diènes obtenus ont permis de synthétiser selon la réaction de Diels-Alder de nouveaux composés carbocycliques et hétérocycliques, difficiles d'accès.
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Lee, Darren Frank. "The catalysed reactions of allyl alcohol using the microporous materials zeolite Y and TS-1." Thesis, University of Liverpool, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.386828.
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Boogaerts, Ine Ida Françoise. "Novel catalysts for the hydroxymethylation of allyl alcohol : a convenient synthetic route to 1, 4-butanediol." Thesis, University of St Andrews, 2009. http://hdl.handle.net/10023/959.
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Hydroxymethylation catalysis provides a valuable strategy for the high volume production of alcohols from α-alkenes. Generally this involves a hydroformylation-hydrogenation sequence, but the capacity to optimise selectivity for each transformation is limited. Condensation reactions between aldehyde products and alcohol products frustrate process economics. By an alternative scheme, all relevant bond-forming reactions occur in a single mechanism. This thesis describes several approaches to catalyst development and the application of derived systems for the hydroxymethylation of allyl alcohol. A review of auto-tandem hydroxymethylation and domino hydroxymethylation is presented in Chapter 1. In Chapter 2 the synthesis of bis-(diethylphosphine) ligands based on a modular series of chiral alicyclic scaffolds is described. High pressure NMR studies have shown that the catalytically active complex [RhH(CO)₂(L-L)] adopts preferentially ea geometry, with [Rh(CO)(L-L)(μ-CO)]₂ as the primary competing species. Catalyst performance can be correlated with the flexibility of the chelating ring; this favoured a high monomer/dimer ratio which enhances activity, but could not rigidify the configuration of the diethylphosphine groups which inhibits linear selectivity. Deuterium labelling studies were suggestive of a domino hydroxymethylation scheme. From the rhodium-hydroxyalkyl-hydride-carbonyl cation, a reductive elimination furnishes the diol derivatives and a β-hydride abstraction furnishes the hydroxyaldehyde derivatives. Up to 53 mol% selectivity to 1, 4-butanediol was attained. The catalysts could be recycled via biphasic separation, however poisoning by methacrolein caused a decline of activity upon reuse of the solution. An investigation of enhanced specific activity via the meta-effect is the subject of Chapter 3. The effect of systematic meta-substitution in triphenylphosphine upon physicochemical properties was investigated by IR spectroscopy and electrochemistry, both of which showed no significant structural impact on the uncoordinated triarylphosphine. Variable temperature ¹H NMR studies however revealed a change in the solution dynamics of the corresponding Vaska complex. The activation barrier to phosphorus-(ipso)carbon rotation increases as a function of meta-substitution, with rotation of substituted aryl rings past each other being more strained. This should create a well-defined coordination sphere around rhodium, and is proposed to account for the high linear selectivity observed in the hydroformylation of allylic alcohols with [RhH(CO){(3, 5-Me₂Ph)P}₃]. Linear-selectivity reached 96 mol%. Catalyst recycling was executed via biphasic separation, retaining on over twelve cycles an average of ~ 94 % efficiency. The kinetics of allyl alcohol hydroformylation with [RhH(CO){(3, 5-Me₂Ph)P}₃] was found to be well represented by Equation 11 (Section 3.6) A detailed analysis of how substrate-specific the influence of the meta-effect remains to be performed. In Chapter 4 domino hydroxymethylation by multi-component L-L/PEt3/Rh systems is described. The regioselective performance of a diphosphine rhodium catalyst in hydroformylation was translated for hydroxymethylation upon introduction of triethylphosphine at a L-L/PEt3 molar ratio ≥ 1. The highest observed selectivity to 1, 4-butanediol was 66 mol%. Competitive activity of triethylphosphine-modified rhodium species presumably accounts for the reduced linear selectivity observed when L-L/PEt3 molar ratio < 1. Despite aggravated catalyst decomposition at higher triethylphosphine concentrations, heterogeneous hydrogenation does not appear to take place. Deuterium labelling studies also discount a sequential homogeneous hydrogenation. There is evidence for the activation of a tris-phosphine-modified rhodium-acyl-carbonyl complex, but such a species could not be isolated from complexation reactions with a variety of precursors. It would be of interest to determine alternative promotors and to establish whether it is preferential to employ a high concentration of mildly acidic species or a low concentration of highly acidic species. The self-assembly of DNA base pair analogues 2-N-pivaloylaminopyridyl phosphine and isoquinolyl phosphine, each modified with diphenylphosphine, diethylphosphine, dicyclohexylphosphine and bis(3, 5-dimethylphenyl)phosphine, is described in Chapter 5. In the presence of a rhodium precursor, exclusive formation of the heteroleptic complex was observed. Although the intramolecular hydrogen-bonding network is sensitive to temperature and free hydroxyl functionalities, highly regioselective catalysts were generally afforded under the appropriate operating conditions. Only the catalyst based on the bis(dicyclohexylphosphine)-heterodimer performed poorly, presumably due to the formation of mono-phosphine complexes. High chemoselectivity was correlated with the heterodimer acidity constant, however this is rendered non-linear by a trans influence when electronic distinction between the platforms is high. Overall, complexes based on the assembly of a dicyclohexylphosphine platform and a bis(3, 5-dimethylphenyl)phosphine platform were found to be optimal; up to 73 mol% selectivity to 1, 4-butanediol was reached. It has been demonstrated in this thesis that in order to effect linear-selective domino hydroxymethylation of allyl alcohol, two distinct transition state structures must be optimised. High regioselectivity demands an asymmetric rhodium-hydride-dicarbonyl complex, which can be generated by an asymmetric chelate or by rigidifying the configuration of the substituents on phosphorus. Interestingly, chelation geometry in this transition state has little impact on this parameter. It has been shown that domino hydroxymethylation is activated by an electron-rich rhodium-acyl-dicarbonyl. The state of electron density on rhodium can be controlled by the substitution pattern on the phosphorus donors, but can also be changed by the inclusion of a suitable promoter. The chelation geometry in this transition state is more significant; placing the acyl functionality trans to a phosphorus donor concentrates the electronic effect in the rhodium-alkyldiol-hydride-carbonyl cation to such an extent as to impede hydride migration and reductive elimination of the diol, favouring β-hydride abstraction and reductive elimination of the hydroxyaldehyde.
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Batt, Frédéric. "Approches synthétiques vers le mycothiazole-4,19-diol : utilisation du palladium en synthèse organique." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00654585.
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Le mycothiazole-4,19-diol, découvert en 2006, est une molécule naturelle isolée de l'éponge marine cacospongia mycofijiensis, dont il n'existe à ce jour aucune synthèse. La structure originale, combinée à la faible abondance naturelle et à une activité biologique potentielle du mycothiazole-4,19-diol font de cette molécule une cible synthétique attractive pour le chimiste organicien et constitue l'objectif de ces travaux de thèse. Le principal enjeu de cette synthèse est la construction du motif diol-1,2 allylique. Au total, quatre déconnections ont été étudiées. Pour chacune d'entre elles, plusieurs approches ont été effectuées afin de construire de manière efficace et élégante le mycothiazole-4,19-diol. Une étude sur l'utilisation du palladium en synthèse organique a également été effectuée au cours cette thèse. Parmi les nombreux systèmes catalytiques dans lesquels ce métal intervient, nous nous sommes intéressés à l'oxydation aérobique des alcools en leurs dérivés carbonylés. Nous avons élaboré un nouveau système permettant l'oxydation sélective des alcools allyliques. Les résultats obtenus sur la haute chimiosélectivité intramoléculaire font de cette méthode un outil puissant et efficace et a été mis à profit dans le cadre des approches du mycothiazole-4,19-diol. Une étude supplémentaire réalisée sur l'utilisation du palladium en réactions séquentielles a également été menée avec l'élaboration d'un processus oxydation aérobique-formation de liaison C-C par couplage de Heck. L'originalité de la méthodologie développée est que le catalyseur intervient dans deux réactions totalement différentes permettant ainsi la synthèse rapide de molécules relativement complexes à partir de substrats simples.
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Kan, Tze-wai Jovi, and 簡紫慧. "Development of new polymer-supported reagents for organic synthesis, solvent effects in samarium promoted allylic alcohol cyclopropanationreactions and time resolved resonance studies of the photodeprotectionof p-hydroxyphenacyl caged phototrigger compounds." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37925660.
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Kan, Tze-wai Jovi. "Development of new polymer-supported reagents for organic synthesis, solvent effects in samarium promoted allylic alcohol cyclopropanation reactions and time resolved resonance studies of the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds." Click to view the E-thesis via HKUTO, 2006. http://sunzi.lib.hku.hk/hkuto/record/B37925660.
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Rahm, Fredrik. "Chiral Pyridine-Containing Ligands for Asymmetric Catalysis. Synthesis and Applications." Doctoral thesis, KTH, Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3564.
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This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.
Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.
Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.
A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.
Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.
Kewords:asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.
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Lemar, Katey M. "Cell death in the human pathogen Candida albicans : effects of garlic (Allium sativum), and garlic constituents allyl alcohol and diallyl disulphide." Thesis, Cardiff University, 2005. http://orca.cf.ac.uk/54550/.
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Garlic extract is very complex, yielding a number of organic sulphur constituents that are thought to be responsible for its anticandidal properties. Many of these are now being investigated in an attempt to determine the mechanisms by which they act. The effects of fresh and freeze dried extracts of
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Gayet, Arnaud. "Development of New Chiral Bicyclic Ligands : Applications in Catalytic Asymmetric Transfer Hydrogenation, Epoxidations, and Epoxide Rearrangements." Doctoral thesis, Uppsala University, Organic Chemistry, 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-4753.
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This thesis describes the synthesis and application of new chiral bicyclic ligands and their application in asymmetric catalysis. The studies involved: [i] The development of novel chiral bicyclic amino sulfur ligands and their use in transfer hydrogenation. [ii] The development of the kinetic resolution of racemic epoxide through the use of chiral lithium amides. [iii] The synthesis and application of chiral bicyclic amine in the organocatalysed epoxidation of alkenes. [iv] Development and application of new chiral diamine ligands in the rearrangement of epoxides into allylic alcohols.
[i] The preparation of two-series of amino thiol ligands based on the structure of camphor is described, together with their application in the iridium-catalysed asymmetric transfer hydrogenation of acetophenone using isopropanol as the hydrogen source. Excellent activity and good enantioselectivity have been achieved using 2 mol% of chiral ligand in combination with [IrCl(COD)]2.
[ii] The chiral diamines (1S,3R,4R)-3-(pyrrolidine-1-ylmethyl)-2-aza-bicyclo[2.2.1]heptane and its (2R,5R)-dimethylpyrrolidine derivative were applied to the kinetic resolution of a variety of racemic 5-7 membered cycloalkene oxides with lithium diisopropylamide (LDA) as the bulk base. Using 5 mol% of the chiral diamines, both unreacted epoxides and allylic alcohols could be produced in enantiomeric excess up to 99%.
[iii] The synthesis of chiral bicyclic amines and their use in the organocatalysed epoxidation of alkene has been described. Using a substoichiometric amount of the chiral amines and aldehydes as ligands precursors, with Oxone® as oxidant, a good activity but moderate enantioselectivity was observed for the epoxidation of trans-stilbene.
[iv] The preparation of 6-substituted-7-bromo-aza-bicyclo[2.2.1]heptanes via nucleophilic addition of organocopper reagents to 3-bromo-1-azoniatricyclo[2.2.1.0]heptyle bromide has been described. These compounds have been utilised as chiral building blocks in the preparation of novel chiral diamine ligands, which have been successfully applied to the catalysed asymmetric rearrangement of epoxide into the corresponding allylic alcohol.
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Guigné, Claire de. "Réactions d'éthers de diénol pour l'accès à des structures terpéniques : condensation carbocationique et métallation vinylique." Rouen, 1997. http://www.theses.fr/1997ROUES034.
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Une nouvelle voie d'accès à des aldéhydes et cétones terpéniques est décrite. Elle est basée sur l'addition électrophile d'alcools allyliques, en présence d'acide, sur des éthers de diénol delta-substitués ou non par un hétéroatome. La synthèse d'éthers de diénol à squelette du prénal portant un substituant en position vinylique ou allylique a été décrite par action d'une base forte sur les acétals alpha, bêta-éthyléniques correspondants, de bons rendements et une très bonne régiosélectivité ont été obtenus. La condensation de ces éthers de diénol sur le carbocation issu d'alcools allyliques permet l'accès au rétinal et à la phytone. Une réaction de métallation en alpha de la fonction éther d'énol a été observée. Une étude portant sur les paramètres influençant la réaction, ainsi que sur l'espèce intermédiaire a permis d'apporter des éléments sur la structure intime des super-bases. L'accès à des éthers de diénol alpha, delta-difonctionnalisés est ainsi réalisée avec de bons rendements.
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Bresciani, Stefano. "Stereospecific dehydroxyfluorination and the synthesis of trifluoro D-hexose sugar analogues." Thesis, University of St Andrews, 2011. http://hdl.handle.net/10023/1878.
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This thesis describes stereospecific fluorination reactions, and addresses the synthesis of fluorosugars. In Chapter 1, the influence of fluorine on the physical properties of organic molecules, as well as its stereoelectronic effects, are introduced. Furthermore, an overview of nucleophilic and electrophilic fluorination reactions is given. Chapter 2 describes the dehydroxyfluorination of allylic alcohol diastereoisomers 155a and 155b, which can proceed either by direct or allylic fluorination. The regio- and stereo- selectivities were also assessed. Chapter 3 outlines the synthesis of the novel trifluoro D-glucose analogue 193 and trifluoro D-altrose analogue 216. The transport of these hexose analogues across the red blood cell membranes was then explored, to investigate the influence of polarity versus hydrogen bonding ability in carbohydrate-protein interactions. Chapter 4 describes the development and optimisation of Bio’s methodology, to promote stereospecific dehydroxyfluorination of benzylic alcohols (R)-213 and (R)-227 by addition of TMS-amine additives 226 and 229. And finally Chapter 5 reports the experimental procedures as well as the characterisation and the crystallographic data of the molecules prepared in this thesis.
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Lima, Luis Ferreira de. "Obten??o de ?lcool al?lico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de ?leo de mamona." Universidade Federal do Rio Grande do Norte, 2012. http://repositorio.ufrn.br:8080/jspui/handle/123456789/13016.
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In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ? C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (? C = C) 1470 -1600 cm -1 and (? CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals
Neste trabalho o biodiesel foi produzido a partir de ?leo de mamona que teve como subproduto a glicerina. A raz?o molar entre ?leo e ?lcool, bem como o uso do (KOH) como catalisador qu?mico para proporcionar a rea??o, foi baseada em dados da literatura. Os melhores resultados foram obtidos, utilizando 1 mol de ?leo de mamona (260g) para 3 mols de ?lcool met?lico (138g). O ?leo utilizado foi adquirido comercialmente, o processo de transesterifica??o envolve a rea??o do ?leo vegetal com um ?lcool met?lico. O produto dessa rea??o ? um ?ster, sendo o biodiesel o seu principal produto e a glicerina o sub-produto a qual foi submetida a tratamento para uso como mat?ria-prima para a obten??o do ?lcool al?lico. A grande vantagem do uso da glicerina para obten??o de ?lcool al?lico ? que sua utiliza??o elimina a grande quantidade de res?duos do biodiesel e v?rias formas de agress?o ao meio ambiente. As rea??es para forma??o do ?lcool alilico foram conduzidas a partir de ?cido f?rmico e glicerina, em uma raz?o 1/1, sob temperatura de 260oC, em uma manta aquecedora, sendo vaporizado por um condensador em espiral por um per?odo de 2 horas, e o produto obtido contem em sua grande maioria o ?lcool al?lico. O acompanhamento das rea??es foi realizado por Espectrofot?metro UV-Vis?vel: FTIR com transformada de Fourier, a an?lise revelou que estas altera??es espectrom?tricas ocorrem indicando a forma??o do produto ?lcool al?lico (prop-2-en-1-ol), em presen?a de ?gua, este ?lcool foi nomeado de ?lcool GL. As bandas de absor??o que confirmam a rea??o foram observadas em (? C=C) em 1470 -1600 cm-1 e em (? C-O), 3610 3670 atribu?das aos grupos C=C e O-H respectivamente. A analise t?rmica foi realizada em um analisador Termogravim?trico SDT Q600, onde a massa e a temperatura ser?o exibidos em fun??o do tempo, isto permite a verifica??o aproximada da taxa de aquecimento. A metodologia inovadora desenvolvida no laborat?rio (LABTAM, UFRN), foi capaz de tratar a glicerina produzida, atrav?s da transesterifica??o de ?leo de mamona e utilizar como mat?ria prima para produ??o do ?lcool al?lico, apresentando um rendimento de 80%, deste ?lcool, o mesmo ? de grande import?ncia na fabrica??o de pol?meros, medicamentos, compostos org?nicos, herbicidas, pesticidas e outros produtos qu?micos
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Santos, Regina Claudia Rodrigues dos. "Catalisadores BimetÃlicos de Ãxidos de MoâCu (Ni ou Co) Suportado em Alumina para ConversÃo do Glicerol a IntermediÃrios QuÃmicos." Universidade Federal do CearÃ, 2016. http://www.teses.ufc.br/tde_busca/arquivo.php?codArquivo=16858.
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Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgicoA viabilidade econÃmica da produÃÃo do biodiesel depende do uso do glicerol, subproduto com estrutura multifuncional, considerado matÃriaâprima bio-renovÃvel, de grande potencial para ser transformado a combustÃveis ou produtos quÃmicos de maior valor agregado. Com o intuito de contribuir para o desenvolvimento dessa linha de pesquisa, foi realizado estudo do potencial catalÃtico da γ-Al2O3 modificada com Ãxido de molibdÃnio e promotores (Cu, Ni ou Co), na reaÃÃo de desidrataÃÃo do glicerol a intermediÃrios quÃmicos com aplicaÃÃo industrial. A estratÃgia foi sintetizar esferas de Al2O3 por mÃtodo hÃbrido, as quais apresentam interessantes propriedades estruturais, texturais e quÃmicas para em seguida impregnar com precursores dos metais via mÃtodo nÃo-convencional (Pechini). A composiÃÃo dos materiais foi escolhida com o objetivo de avaliar o efeito bifuncional causado pela combinaÃÃo das propriedades Ãcido/bÃsicas e redox de catalisadores de molibdÃnio suportado em alumina. Para fins comparativos foi testado catalisador comercial Ni-Mo/Al2O3 com elevada acidez e porosidade. Os catalisadores foram caracterizados por: ICP-OES, FRX, TGA/DTA, DRX, MEV, IV, TPR-H2, TPD-CO2, isotermas de adsorÃÃo/dessorÃÃo de N2, e acidez atravÃs de adsorÃÃo de piridina. O desempenho dos catalisadores foi avaliado na desidrataÃÃo do glicerol, sob fluxo de N2 ou H2, a 1atm e 250ÂC. As mudanÃas na atividade e seletividade devido à troca do gÃs de arraste estÃo associadas a alteraÃÃes nas propriedades Ãcido/redox dos catalisadores, como sugerido pelas medidas de acidez e TPR-H2. AcroleÃna foi o principal produto observado para todos os catalisadores, porÃm a amostra contendo cobre (CuMoAl), mostrou maior atividade catalÃtica e superior seletividade a Ãlcool alÃlico, bem como produÃÃo do 1-propanol; o que està associado a transferÃncia de hidrogÃnio. Essa seletividade concorda com resultados de TPR-H2, que mostram maior influÃncia do cobre sobre a reduÃÃo do Ãxido de molibdÃnio, quando comparado aos promotores (Co ou Ni). Ao final sÃo propostos passos reacionais envolvidos na conversÃo do glicerol a Ãlcool alÃlico.
The economic viability of biodiesel production depends of the use of glycerol, by-product with multifunctional structure, considered a bio-renewable feedstock of great potential to be transformed to fuel or higher value-added chemicals products. In order to contribute to the development of this research area, study was carried out in order to explore the catalytic potential γ-Al2O3 modified with molybdenum oxide and promoter (Cu, Ni or Co) in the glycerol dehydration reaction to chemical intermediates with industrial application was performed. The strategy was to synthesize Al2O3 spheres by hybrid method with interesting structural, textural and chemical properties for then impregnating with precursors of metals via unconventional method (Pechini). The material composition was chosen with the aim of evaluating the bifunctional effect caused by the combination of acid-base and redox properties of molybdenum catalysts supported on alumina. For comparison was evaluated commercial Ni-Mo/Al2O3 catalyst with high acidity and porosidade. The catalysts were characterized for: ICP-OES, XRF, TGA/DTA, XRD, SEM, IR, H2-TPR, TPD-CO2, N2 adsorption/desorption isotherms, and acidity measurements through pyridine adsorption. The catalytic performance was evaluated in the glycerol dehydration under N2 or H2 flow at atmospheric pressure and 250ÂC. The modification in the activity and selectivity due to the change of carrier gas are attributed to the changes of acid/redox properties of the catalyst, as suggested by acidity measurements and TPR-H2. Acrolein was the main product observed for all catalysts, but the cupper containing catalyst (CuMoAl) showed higher catalytic activity and, and superior selectivity to allyl alcohol, as well as the production of 1-propanol, which is due to the hydrogen transfer. This selectivity agrees with H2-TPR results, which show stronger effect of the copper over the molybdenum oxide reduction, if compared to the others promoter (Co or Ni). At the end it is proposed the reaction steps mechanism for the glycerol conversion to allyl alcohol.
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Iloughmane-Gaspard, Hafida. "Ene reactivite d'alcenylsilanes et -germanes : synthese et stabilisation de metalloles du groupe 14." Toulouse 3, 1986. http://www.theses.fr/1986TOU30214.
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La synthese d'alcools allyliques organometalliques du groupe 14 (si,ge) a ete effectuee par oxydation de composes ethyleniques (photo-oxygenation ; epoxydation/rearrangement). Ces alcools ou leurs esters ont ete valorises en tant que precurseurs des premiers metalloles, isologues des cyclopentadienes, c-non substitues ou c-methyles qui ont ete stabilises par complexation-pi (fe,co). L'auteur decrit plus de 100 produits organometalliques nouveaux dont les structures moleculaires sont etablies par spectrometries de resonance magnetique nucleaire, de masse, photo-electronique et de diffraction des rayons x. Les mecanismes des reactions de cycloaddition, d'oxydation et d'elimination mises en jeu au cours de ce travail sont discutes
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Legoupy, Stéphanie. "Synthèse et réactivité de nouveaux complexes organométalliques chiraux du rhénium." Rennes 1, 1997. http://www.theses.fr/1997REN10148.
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Le travail présenté dans ce mémoire concerne la synthèse et la réactivité de complexes du rhénium. De nouveaux complexes organométalliques chiraux du rhénium des alcools propargyliques et homoallylique ont été synthétisés. Des alcools allyliques secondaires et 1,2-disubstitues ont été coordonnés à l'entité chirale (#5C#5H#5)Re(No)(Pph#3)#+Bf#4#-. Dans le cas du 3-buten-2-ol complexe, les deux diastéréoisomères ont pu été séparés. L'étude de la réactivité de ces complexes du rhénium a montré qu'ils sont compatibles avec des réactions d'oxydation, de Wittig, de réduction, d'estérification, de chloration, de bromation et de fluoration. L'entité organométallique (#5C#5H#5)Re(No)(Pph#3)#+Bf#4#- s'est montrée un bon groupement protecteur d'une seule double liaison au cours de ces réactions. Les substitutions allyliques, catalysées par un acide de Lewis, sur les complexes du rhénium des alcools allyiques ont été étudiées. Quelque soit le nucléophile, ces réactions sont régio- et stéréosélectives et se font avec rétention de configuration. Un mécanisme impliquant un complexe -allyl dicationique du rhénium a été proposé. Le rôle activateur du rhénium a été mis en évidence.
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Benhaddou, Rachida. "Arylation de doubles liaisons catalyses par le palladium : influence de differents facteurs sur la cinetique de la reaction, etude de nouvelles syntheses d'aryl-c-glycosides." Paris 6, 1988. http://www.theses.fr/1988PA066065.
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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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Chavant, Pierre Yves. "Reaction de type barbier ou reformatsky effectuees a l'aide de manganese." Paris 6, 1988. http://www.theses.fr/1988PA066138.
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Etude de la reactivite du manganese metallique vis-a-vis d'halogenures allyliques et d'halogeno-2 esters. Une etude de l'influence du solvant et de la presence de divers sels metalliques, a debouche sur la mise au point d'une nouvelle voie d'acces a des alcools homoallyliques
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Souchet, Michel. "Synthese de la (+) anticapsine et d'analogues structuraux : evaluation de leurs proprietes biologiques." Paris 6, 1988. http://www.theses.fr/1988PA066545.
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Synthese du compose du titre et de ses derives perhydro indoliques via la synthese stereoselective d'alcools allyliques. Etude de l'activite inhibatrice des composes synthetises sur la glucosamine synthetase et sur l'enzyme de conversion de l'angiotensine
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Alvarez, Gonzalez Eleuterio. "Substitution d'ethers et d'alcools allyliques par differents nucleophiles en presence de complexes de nickel(0) : synthese stereoselective des dienes-1,4 a partir des sulfones dieniques avec le chlorure d'isopropylmagnesium en presence de sels de." Paris 6, 1987. http://www.theses.fr/1987PA066064.
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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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Touma, Marwan. "Nouvelles reactions d'oligomerisation et de telomerisation selectives catalysees par des complexes cationiques du palladium." Toulouse 3, 1986. http://www.theses.fr/1986TOU30139.
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PETIT, YVES. "Synthese d'hydroxy-2 esters enantiomeriquement purs a partir d'amino-2 acide : etude stereochimique de l'addition 1,4 d'organometalliques sur des systemes insatures-2,3 hydroxy-4." Paris 6, 1987. http://www.theses.fr/1987PA066578.
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Hesse, Andrew J. "Nontraditional synthesis of organometallic compounds and allylic alcohols /." 2007. http://digitalcommons.butler.edu/ugtheses/52/.
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Huang, Chung-wei, and 黃宗煒. "Stereo- and Regioselectivity in Palladium-Catalyzed Allylic Amination by Direct Use of Allyl Alcohols." Thesis, 1999. http://ndltd.ncl.edu.tw/handle/92697331666380599815.
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碩士高雄醫學院
藥學研究所
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Allylic amines are an important class of compounds not only their utility as intermediate in organic synthesis but also because of their physiological properties and their presence in several natural products. Allylation of carbon-, nitrogen-, and oxygen-nucleophiles catalyzed by palladium complexes has been widely applied to organic synthesis. There have been only limited and sporadic reports dealing with the direct cleavage of the C-O bond in allyl alcohols on interaction with a transition metal complex. Precedents of successful applications of a process using allyl alcohols directly to catalytic processes are even more limited. During the course of our studies on the formation of the carbon-nitrogen bond via the O-amination of allyl alcohols in the presence of palladium(0) complexes, we found that the use of anilines as the nucleophiles was a very simple and valuable synthetic route to N-allylanilines. The alkoxides appear to enhance the reactivity of allyl alcohols toward palladium(0) species. We considered that, when anilines are employed as nucleophiles for thereaction, a convenient method to prepare N-allylanilines could be realized; the anilines are useful compounds in organic synthesis. We have examined the reaction of allyl alcohols with anilines in the presence of a palladium catalyst and titanium(IV) isopropoxide. This result prompted us to study in detail the direct use of allyl alcohols with anilines in the presence of a palladium catalyst and titanium(IV) isopropoxide in order to understand the main factors affecting the regio- and stereocontrol of the reaction; this is important for practical synthetic applications and also for gaining more insight into the mechanism.
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Jang, Gwo Ming, and 曾國銘. "Microwave Assised Cycloaddition Reaction of Allylic alcohols and Nitrile Oxides." Thesis, 1998. http://ndltd.ncl.edu.tw/handle/74173902127574287473.
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