Дисертації з теми "Hydroformylation of Alkenes"
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Iu, Leo. "New catalysts for branched selective hydroformylation of alkenes." Thesis, University of St Andrews, 2019. http://hdl.handle.net/10023/17068.
Повний текст джерелаOsuna, Anna Maria Banet. "Hydroformylation of higher and functionalised alkenes in supercritical carbon dioxide." Thesis, University of Liverpool, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.343988.
Повний текст джерелаAnnis, Alexandra H. "The Development of Rhodium-Catalyzed Asymmetric Hydroformylation of 1-Alkenes to Access Chiral Aldehydes." Thesis, Boston College, 2015. http://hdl.handle.net/2345/bc-ir:104636.
Повний текст джерелаAsymmetric hydroformylation (AHF) is a metal-catalyzed reaction in which CO and H2 are added across an olefin to form a new carbon-carbon bond. AHF has perfect atom-economy and is an ideal way to form a chiral aldehyde. However, the utility of branch selective hydroformylation is limited due to a lack of readily available ligands and restrictions on a wide variety of terminal olefins. Herein, Rh-catalyzed asymmetric hydroformylation of 1-alkenes is reported using commercially available Ph-BPE ligand to generate α-chiral aldehydes. A wide range of terminal olefins were explored and all showed high enantioselectivity (up to 98:2 er) and good regioselectivity (up to 15:1 branched to linear ratio)
Thesis (MS) — Boston College, 2015
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Desset, Simon L. "New strategies for the rhodium-catalysed aqeous-biphasic hydroformylation of medium chain alkenes /." St Andrews, 2009. http://hdl.handle.net/10023/842.
Повний текст джерелаDesset, Simon L. "New strategies for the rhodium-catalysed aqueous-biphasic hydroformylation of medium chain alkenes." Thesis, University of St Andrews, 2009. http://hdl.handle.net/10023/842.
Повний текст джерелаGong, Zhenxin. "Continuous flow homogeneous hydroformylation of 1-octene over supported ionic liquid phase rhodium catalysts using supercritical CO₂." Thesis, University of St Andrews, 2011. http://hdl.handle.net/10023/1877.
Повний текст джерелаBronger, Raymond Petrus Johannes. "Selective hydroformylation of internal alkenes to linear aldehydes novel phosphacyclic diphosphines and their applications /." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2004. http://dare.uva.nl/document/75911.
Повний текст джерелаSun, Xixi. "Scaffolding Catalysis: Towards Regioselective Hydroformylation of Alkenes and Site-Selective Functionalization of Polyhydroxylated Molecules." Thesis, Boston College, 2013. http://hdl.handle.net/2345/3324.
Повний текст джерелаChapter 1. We reported the first synthesis of all-carbon quaternary centers via hydroformylations using a catalytic directing group. With the ability of reversibly and covalently binding to a substrate, and coordinating to a metal center, scaffolding catalyst 1.1 is able to direct the branch-selective hydroformylation of 1,1-disubstituted olefins under mild temperature. Chapter 2. We have designed and synthesized a chiral organocatalyst 2.11. This catalyst is able to covalently bind to one hydroxyl, and utilize the induced intramolecularity to stereoselectively functionalize the other hydroxyl within a cis-1,2-diol via electrophile transfer. Catalyst 2.11 was used in the desymmetrization of meso-1,2-diols under mild conditions (4 C to room temperature), leading to high yields and selectivities for a broad substrate scope. Chapter 3. Catalyst 3.1 and 3.6 were demonstrated to selectively bind to primary hydroxyls over secondary hydroxyls. By combining the binding selectivity with asymmetric catalysis, these scaffolding catalysts were shown to promote the selective silylation of secondary hydroxyls within terminal (S)-1,2-diols. The reversal of substrate bias was further applied to a regiodivergent kinetic resolution of racemic terminal 1,2-diols, producing secondary protected products in synthetically practical levels of enantioselectivity (>95:5 er) and yields (≥40%). Time course studies of this reaction further revealed the optimal condition to form the primary silylated product in high s-factor. Chapter 4. Based on the previous understanding of catalyst 4.5 and 4.6, the exclusive catalyst recognition of cis-1,2-diols within polyhydroxylated molecules was further discovered. This unique functional group display recognition was further allied with the catalyst's ability to stereoselectively differentiate hydroxyls within cis-1,2-diols, enabling the site-selective protection, functionalization, and activation of the inherently less reactive axial hydroxyl groups within carbohydrates. This methodology also enables the selective functionalization of multiple complex molecules, including digoxin, mupirocin, and ribonucleosides, demonstrating the potential power of scaffolding catalysis in the rapid access to valuable synthetic derivatives of polyhydroxylated compounds
Thesis (PhD) — Boston College, 2013
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Guo, Ipin. "Hydroformylation of olefins by water soluble and asymmetric cobalt and platinum complexes." Diss., Virginia Tech, 1991. http://hdl.handle.net/10919/39855.
Повний текст джерелаPh. D.
Du, Toit Judith G. O. "Use of water-soluble phosphine ligands in heterogeneous hydroformylation catalysis : application to long-chain 1-alkenes." Master's thesis, University of Cape Town, 1994. http://hdl.handle.net/11427/22055.
Повний текст джерелаPogrzeba, Tobias [Verfasser], Reinhard [Akademischer Betreuer] Schomäcker, Reinhard [Gutachter] Schomäcker, and Dieter [Gutachter] Vogt. "Rhodium-catalysed hydroformylation of long-chain alkenes in aqueous multiphase systems: Kinetic studies and systematic process development / Tobias Pogrzeba ; Gutachter: Reinhard Schomäcker, Dieter Vogt ; Betreuer: Reinhard Schomäcker." Berlin : Technische Universität Berlin, 2018. http://d-nb.info/1156354110/34.
Повний текст джерелаGarcia, Marco Aurélio Suller. "Nanopartículas de Ródio: componentes para a preparação de catalisadores para reações de hidroformilação de olefinas." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-30112016-104332/.
Повний текст джерелаThe importance of catalysis to society may be seen in numbers: 90% of chemical production processes and more than 20% of all industrial products sold in the world use one or more catalytic steps. Thus, the development of efficient, active, and selective catalysts is crucial for creating cleaner and sustainable technologies. In addition, chemical reactions that generate new C-C bonds are among the most important transformations in organic chemistry and are the basis of this work. Rhodium catalysts presented herein are part of a careful investigation, which included the development, synthesis and characterization of metal nanoparticles and magnetic functional supports for use in the transformation of various molecules. The initial study of supported rhodium nanoparticles in cyclohexene hydrogenation reactions has driven our understanding of the behavior of these nanostructures, and the influence that different ligands and stabilizers may have in a well-known catalytic application. The identification of a highly active and recyclable catalytic system aroused our interest for its improvement for application in hydroformylation reactions. Prior to the synthesis of supported catalysts, studies with non-supported nanoparticles revealed that a modified system with the addition of phosphines was required for activation of the catalyst and the stabilizer used affected the catalytic activity. Thus, to enable efficient immobilization of the active species, the surface of the magnetic support was modified with methyldiphenylphosphine. The catalyst preparation removed, at least partially, the stabilizer adsorbed on the nanoparticles surfaces. The phosphine-functionalized support anchored the active species and avoided their leaching, allowing the reuse of the catalyst. The hydroformylation reaction of oct-1-ene reached 96% of conversion and 82% of selectivity to aldehydes, in 6 hours at 80°C. The metal loading of the catalyst was only 0.2%. Seeking to increase the efficiency in metal immobilization step and a better catalytic activity that would enable the use of more complex substrates, the magnetic support was modified with a hyperbranched polymer, which allowed an increase in the amount of external phosphines, as well as a significant increase in metal loading on the support. The hydroformylation reaction of natural products was possible and, with the estragole compound, 100% of conversion was achieved in 6 hours with 70% of selectivity to aldehydes. Despite evidence that suggests the formation of active molecular species, the modified support has enabled the catalyst to retain its activity and selectivity for at least six successive reactions. The materials developed could be handled in air without damaging their catalytic activity, durability and separation properties.
Yildiz, Ünveren Hesna Hülya. "Hydroformylation of long chain olefins in microemulsion." [S.l.] : [s.n.], 2004. http://deposit.ddb.de/cgi-bin/dokserv?idn=972892109.
Повний текст джерелаEpton, Jeremy W. "Alkene hydroformylation catalysed by dinuclear rhodium complexes." Thesis, Kingston University, 1990. http://eprints.kingston.ac.uk/20536/.
Повний текст джерелаKistamurthy, Deshen. "An investigation into the alkene hydroformylation reaction using platinum complexes." Master's thesis, University of Cape Town, 2009. http://hdl.handle.net/11427/9278.
Повний текст джерелаHydroformylation is the most widely applied homogeneous catalysis reaction used in industry. The aldehyde product is an important commodity in both the bulk and specialty chemical industry. Platinum catalysts have shown significant chemo- and regioselectivities in alkene hydroformylation. This thesis investigates the activity as well as selectivity of platinum complexes containing bidentate ligands in the hydroformylation reaction.
October, Jacquin. "Novel multinuclear complexes of Rh and Ru and their application in alkene hydroformylation." Thesis, Stellenbosch : Stellenbosch University, 2015. http://hdl.handle.net/10019.1/97866.
Повний текст джерелаENGLISH ABSTRACT: This project entailed the synthesis and characterization of mono- and multi-nuclear rhodium and ruthenium iminopyridyl complexes and their application in the hydroformylation of 1- octene. The multi-nuclear complexes were synthesized in order to investigate whether it could produce catalysts with higher activity than their mononuclear analogues. Four novel iminopyridyl ligands, ranging from mono- to tetra-functional compounds, were synthesized. The synthesis was a two-step process initially involving a Schiff base condensation reaction between 2-pyridinecarboxaldehyde and 4-aminophenol to produce a hydroxy functionalized pyridine-imine. The latter was then subjected to a nucleophilic substitution reaction with an appropriate benzyl bromide derivative to yield the target ligands. All these ligands were isolated in moderate to good yields and characterized using a range of analytical techniques. These ligands, together with the hydroxy functionalized pyridine imine, were then complexed to both Rh(I) and Ru(II) metal precursors, yielding ten novel metal complexes. The characterization of some of the complexes, especially the multi-nuclear complexes, were slightly more difficult due to their low solubility. However, all these complexes could be isolated in good to high yields as stable green-brown (in the case of Rh(I)) and yellow-orange (in the case of Ru(II)) solids. Finally, these complexes were applied as catalyst precursors in the hydroformylation of 1- octene. In the case of the Rh(I) complexes, relatively high activities were observed, with conversions ranging between 50 – 90 % in all cases, when tested at 30 bar, 75 °C and a 0.05 mol% catalyst loading. The activity was found to increase when going from the mono- to the bi-nuclear catalyst. However, solubility in the reaction medium was a major issue for the trinuclear catalyst, as it contributed to the lower activity observed. High chemoselectivity towards aldehydes was observed for all catalysts, which increased with reaction times. During shorter reaction time, linear regioselectivity was also relatively high. This however, decreased with increasing reaction time as the internal octenes formed initially, were converted to branched aldehydes. When the Ru(II) complexes were tested under the same conditions as the Rh(I) complexes, very low activity was observed. Under more stringent conditions (45 bar, 120 °C, 0.5 mol%) the ruthenium catalysts performed relatively well, compared to other complexes in the literature. The same trend in terms of the chemo- and regioselectivity for the Ru(II) complexes were observed. The Rh(I) complexes were far more active than the Ru(II) complexes.
AFRIKAANSE OPSOMMING: Hierdie projek behels die sintese en karakterisering van mono- en multi-kernige rhodium en ruthenium iminopiridiel komplekse en hul toepassing in the hidroformulering van 1-okteen. Die multi-kernige komplekse is gesintetiseer met die doel om vas te stel of hulle katalisatore wat meer aktief is as hul monokernige eweknieë, kan produseer. Vier nuwe iminopiridiel ligande, wat strek vanaf mono- tot tetra-funksionele verbindings, is gesintetiseer. Die sintese was ‘n twee-stap proses wat aanvanklik ‘n Schiff basis kondensasie reaksie tussen 2-piridienaldehied en 4-aminofenol behels, om ‘n fenol gefunksioneerde piridien-imien te vorm. Die laasgenoemde was gevolglik aan ‘n nukleofiliese substitusie reaksie met ‘n gepaste bensiel bromied derivaat onderhewig. Al hierdie ligande is geisoleer in matige tot goeie opbrengste en gekarakteriseer met ‘n reeks analitiese tegnieke. Hierdie ligande, tesame met die fenol gefunksioneerde piridien imien, is dan met Rh(I) en Ru(II) metaal uitgangstowwe gekomplekseer, wat tien nuwe metaal komplekse tot gevolg gehad het. Die karakterisering van sommige van die kompekse, spesifiek die multi-kernige komplekse, was effens moeiliker as gevolg van hul swak oplosbaarheid. Al hierdie komplekse kon egter in goeie tot hoë opbrengste as stabiele groen-bruin (in die geval van Rh(I)) en geel-oranje (in die geval van Ru(II)) vastestowwe geisoleer word. Laastens is die komplekse as katalisator-voorlopers in die hidroformulering van 1-okteen gebruik. In die geval van die Rh(I) komplekse is redelike hoë aktiwiteite waargeneem, met omsettings tussen 50 – 90 % in alle gevalle, wanneer hulle by 30 bar, 75 °C en ‘n katalisator lading van 0.05 mol% getoets is. Die aktiwiteit neem toe vanaf die mono- na die bi-kernige katalisator. Oplosbaarheid in die reaksie medium was egter ‘n probleem vir die tri-kernige katalisator, wat ‘n laer aktiwiteit tot gevolg gehad het. Hoë chemoselektiwiteit na aldehiede is waargeneem vir al die katalisatore en dit neem toe met reaksietyd. Gedurende korter reaksietye was die liniêre regioselektiwiteit ook redelik hoog, maar neem af met toenemende reaksietyd soos die interne okteen wat aanvanklik vorm na vertakte aldehiede omgeskakel word. Toe die Ru(II) komplekse onder dieselfde toestande as die Rh(I) komplekse getoets is, was baie lae aktiwiteite waargeneem. Onder hoër temperatuur en druk (45 bar, 120 °C, 0.5 mol%) toon die ruthenium katalisatore redelik goeie aktiwiteite in vergelyking met ander komplekse wat in die literatuur gerapporteer is. Dieselfde tendense in terme van die chemoen regioselektiwiteit is vir die Ru(II) komplekse waargeneem. Die Rh(I) kompleks was baie meer aktief as die Ru(II) komplekse.
Obrecht, Lorenz. "Artificial metalloenzymes in catalysis." Thesis, University of St Andrews, 2015. http://hdl.handle.net/10023/7248.
Повний текст джерелаStitou, Bachir. "Emploi de nouveaux systemes catalytiques pour la carbonylation d'alcenes et de substrats insatures fonctionnalises." Toulouse 3, 1988. http://www.theses.fr/1988TOU30028.
Повний текст джерела"Nano-space confinement of pre-selective catalysts for hydroformylation of 1-octene." Thesis, 2015. http://hdl.handle.net/10210/14155.
Повний текст джерелаRhodium-catalyzed hydroformylation is one of the most important industrial processes for the production of linear and branch aldehydes. Aldehydes serve as intermediates in the production of various fine chemicals. Rh-based homogeneous catalysts for aldehydes production have demonstrated high yields and selectivity. Catalyst separation and recovery of expensive Rh-metal from reaction mixtures is a challenge to this process. With increasing industrial demand for highly selective processes, homogeneous catalysis could well be extensively employed if catalyst recovery from products and recyclability could be accomplished more efficiently and economically. The above problems justify the investigation of immobilized (heterogenized) catalysts by both academia and industry. This would solve the separation problem by making it possible to separate the catalyst from the reaction medium with simple filtration techniques and to regenerate the catalyst for reuse. Moreover, the ease of recovery of catalyst from products and reusability can minimize the impact of the process on the environment. Immobilization of metal complexes on solid supports is an effective approach to overcome the limitations of homogeneous catalysis. Support materials such as Mobil Composite Material (MCM-41) and Santa Barbara Amorphous type material (SBA-15) are attractive candidates for immobilizing metal complexes because of their high surface area, adjustable pore sizes, large pore volumes and high surface silanol groups. In the present work, mesoporous silica supports, MCM-41 and SBA-15 were synthesized. Rhodium(I) complex species, trans-aquacarbonyl bis(triphenylphosphine) [Rh(CO)(OH2)(PPh3)2]OTf and trans-aquacarbonyl bis{tris-(m-sulfonphenyl)-phosphine} [Rh(CO)(OH2)(TPPTS)2]OTf were synthesized as catalyst precursors and anchored onto the mesoporous MCM-41 and SBA-15 framework structure via an electrostatic method to form immobilized (heterogenized) catalysts. The support and catalyst were characterized using a range of solid-state techniques. Results showed that the structural integrity of the catalyst supports was maintained after immobilization. Results also revealed a strong interaction between rhodium complex species and the inner walls of the ordered mesoporous materials, thus leading to the formation of stable heterogenized catalysts. In addition, immobilized catalysts constrained the pores, thus leading to a confinement effect, which enhanced activity and regioselectivity in the hydroformylation process. Selected immobilized catalysts were...
Ferreira, Alta Carina. "Transition metal catalysed carbonylation reactions in organic synthesis." Thesis, 2008. http://hdl.handle.net/10210/348.
Повний текст джерелаProf. C.W. Holzapfel
Fagan, Maureen A. "I. kinetics and thermodynamics of alkene complexation in d⁰ yttrium-alkyl-alkene complexes II. mechanism of the reversal of enantioselectivity in the platinum-catalyzed hydroformylation of styrene." 1999. http://www.library.wisc.edu/databases/connect/dissertations.html.
Повний текст джерелаHsu, Kuo-Hsun, and 徐國訓. "Investigation on Rh-catalyzed Hydroformylation Domino Bicyclization bearing a Trisubstituted Alkene Moiety as the Carbon nucleophile and Mechanistic Study on a novel Rh-catalyzed Hydrogen-free Lactamization." Thesis, 2016. http://ndltd.ncl.edu.tw/handle/40310092092849871774.
Повний текст джерела國立中興大學
化學系所
104
We describes the investigation of Rh-catalyzed domino hydroformylation bicyclization, which has been developed for preparation of bicyclic alkaloid skeletons. The first part we used trisubstituted alkene-mediated domino hydroformylation bicyclization to synthesize of Epiquinamide and Epiepiquinamide in five steps (35% overall yield). The second part we mechanistic study on a novel Rh-catalyzed hydrogen-free lactamization. The third part we describes the influence of the alkene during amides preparation.