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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
211

The corrole ring : synthesis, functionalisation and reactions of a biomimetic macrocycle.

Zipp, Caitlin 04 March 2014 (has links)
The lability of cobalt(III) in vitamin B12 is thought to come about as a function of its coordination environment. The thermodynamics and kinetics of ligand substitution reactions of vitamin B12a were compared to those of a synthetic, more electron rich, corrole-based biomimetic model. The feasibility of corrole synthesis was established with the synthesis of several corroles with different meso substituents. The biomimetic model was designed such that the central meso position bore a substituent with a terminal imidazole (referred to as the ‘tail’) which might act as an axial ligand for a coordinated cobalt ion while the remaining two meso positions bore water-solubilising glucose substituents. Unfortunately, the biomimetic model was water soluble below pH 4 only. This rendered the model unsuitable for the present study and these water solubilising groups were not incorporated into the final model. The model system used in this work is [10-(2-{[4-(1Himidazol-1-ylmethyl)benzoyl]amino}phenyl)-5,15-diphenylcorrolato]cobalt(III), referred to as DPTC-Co Intermediates of the ‘tail’ meso substituent were found to be polymorphic and five pairs of polymorphs were identified. Polymorphism arose from differences in weak termolecular forces and these differences were evaluated. The stability constants for the binding of various neutral N-, P- and S-donor ligands and anionic N-, S-, I- and C-donor ligands to both vitamin B12a and DPTC-Co were determined in a buffered 80:20 methanol:water solvent system. The more stable binding of neutral ligands to DPTC-Co and anionic ligands to vitamin B12a indicates that the interaction between the metal and an incoming ligand is indeed affected by the metal’s coordination environment. Cobalt(III) in DPTC-Co appeared to favour softer ligands while harder ligands were favoured by vitamin B12a. Kinetic studies showed that the coordination of cyanide to cobalt in vitamin B12a was faster than in DPTC-Co. The reaction between cyanide and vitamin B12a was found to be entropically driven while the reaction with DPTC-Co was enthalpically driven. This suggests that while the reaction between cyanide and vitamin B12a is faster, the reaction between cyanide and DPTC-Co is electronically more labile. The coordination environment of cobalt has been seen to significantly affect its chemistry. Coordination by the more electron rich corrole macrocycle led to a softer and more electronically labile metal then when coordinated by the corrin macrocycle of vitamin B12a.
212

The Discovery and Development of Metal-Free Arylation Reactions with Unsymmetrical Diaryliodonium Salts

Sundalam, Sunil Kumar 08 August 2017 (has links)
Functionalizing arenes and heteroarenes has been an active area of research since the 19th century, due to the presence of these molecular structures in many industrially important sectors. A tremendous amount of research has been published in achieving these chemical transformations using stoichiometric reagents and transition metal-catalyzed reactions. However, challenges still remain. An alternative and comparable methodology to metal-catalyzed reactions to overcome the drawbacks will advance this particular area of research is desirable. Hypervalent iodine compounds offer a promising approach to metal-free arylation reactions. These mild, air and moisture stable compounds have showed significant success as non-toxic and metal-free reagents for the arylation reactions. In particular, unsymmetrical diaryliodonium salts offer functionalization of complex arene structure in an efficient and sustainable pathway. A base-mediated coupling reaction for the metal-free synthesis of alkyl-aryl ethers by using unsymmetrical diaryliodonium salts and aliphatic alcohols is described. This method shows broad substrate scope with respect to both of the coupling partners to produce industrially useful alkyl-aryl ethers in moderate to excellent yields. The reaction is operationally simple, proceeds at mild temperature, and is atom-economical. Sustainability and synthetic utility of this reaction is demonstrated by the use of unsymmetrical aryl(mesityl)iodonium salts as the arylating agents. A limitation of poor reactivity of electron rich unsymmetrical diaryliodonium salts was overcome by designing 2nd generation conditions and using trimethoxy benzene (TMP) as the auxiliary group. Additionally discovery and development of an efficient method to access highly functionalized arynes from unsymmetrical aryl(mesityl)iodonium tosylate salts is presented. The aryne intermediates are generated by ortho C-H deprotonation of aryl(mesityl)iodonium salt with an amide base and subsequently trapped in a cycloaddition reaction with furan in moderate to good yields. Selective iodonium moiety elimination is discussed and the effect of auxiliary and temperature to reduce the regioisomeric ratio is demonstrated. Finally, additional coupling partner including benzyl azide and aliphatic amines are presented to show further utility of this methodology. Also, mechanistic investigations leading to the moderate reactivity of some electron rich unsymmetrical diaryliodonium salts is discussed.
213

The Preparation of Diaryliodonium Salts for Application in Arylation Chemistry

Seidl, Thomas Ludwig 02 April 2018 (has links)
Diaryliodonium salts offer potential as novel reagents for arylation chemistry. An overall goal and successful outcome of this work has been to further understanding of diaryliodonium salt chemistry by developing practical methods that enable chemists more convenient access to these reagents, for the purpose of reaction development. To this end a robust and convenient preparation method has been developed and resulted in novel commercially available diaryliodonium salts. The remainder of the work described, has focused on understanding the parameters important to diaryliodonium mediated arylation and has resulted in a solid framework that multiple future development efforts can build upon. A strategy adopted throughout this work was to use multivariate methodologies such as Design of Experiments (DoE). Applicable chapters show the results of optimization studies that were carried out using DoE, during the course of this work. Additionally, the desire to further realize the potential that DoE has to offer inspired of a search for parameters to study fundamental reactivity. Chapter 2 details the development of a practical diaryliodonium salt synthesis that is convenient, facile, and economical. A detailed procedure is also included and was drafted to the requirements for publication in the journal Organic Synthesis. Finally, limitations and future directions of the method are discussed. Chapter 3 describes studies aimed at understanding the role of the counter anion; a very practical counter anion screening method is presented. Future directions are discussed and include detailed characterization of diaryliodonium salts by NMR. Chapter 3 also describes a practical, scalable, and rapid salt exchange method developed during this work. Chapter 4 describes the results obtained in studying an azidation reaction via solubility parameters. All Supporting Information, including characterization data and experimental details, are provided in Chapter 5.
214

Preliminary studies for the synthesis of analogues of batrachotoxinin A

Yang-Chung, Guy January 1974 (has links)
No description available.
215

Synthesis of compounds of natural and unnatural origin by intramolecular alkylations

Shirley, Neil John. January 1987 (has links) (PDF)
Bibliography: leaves 213-223.
216

Studies toward the total synthesis of (+)-cortistatin J via an intramolecular (4+3) cycloaddition

Liu, Lok-lok., 廖樂樂. January 2011 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
217

Asymmetric reactions induced by phase-tagged phosphoric acid organocatalysts and copper hydride-catalyzed reductions of unsaturatedthioesters

Ou, Jun, 欧军 January 2011 (has links)
Two syntheses of non-cross-linked polystyrene-supported TADDOL-based phosphoric acid organocatalyst have been developed. The optimal polymer-supported catalyst 2.29d exhibited comparable catalytic activity to its small molecule counterpart in asymmetric Mannich-type reactions, and the syntheses of several chiral β-amino esters were demonstrated using 2.29d as catalyst. However, when this TADDOL-based phosphoric acid was immobilized on a polystyrene cross-linked with 1,4-bis(4-vinylphenoxy)butane, ie. JandaJelTM, the catalytic activity diminished in the first recycling and reuse of the catalyst. Building on the success of the immobilization of chiral phosphoric acid, a more robust phase-tagged BINOL-based phosphoric acid organocatalyst was developed. By taking advantage of a tetraarylphosphonium salt as a solubility-controlling group, a widely-used BINOL-based phosphoric acid, TRIP (3.1), was introduced onto a tetraphenylphosphonium salt to produce a phosphonium salt-tagged phosphoric acid catalyst 3.3e. After systematic optimizations of reaction conditions, it was found that the catalyst 3.3e with PF6 as counteranion exhibited the best performance in terms of enantioselectivity. Catalyst 3.3e was proved to be highly effective in asymmetric Friedel-Crafts reaction of indoles because it was shown to be recyclable and reusable after six cycles without loss of catalytic activity. Based on our previous studies on the reduction of unsaturated thioesters catalyzed by (BDP)CuH, further investigation of ligand effects revealed that in addition to BDP, dppf was also an effective ligand for the simple reduction of 5.8. In the stoichiometric reduction of unsaturated thioester 5.8, dppe and dppf were both efficient ligands for copper hydride that could convert 5.8 to aldehyde 5.18 in the presence of TMSCl, without the formation of the undesired enol ester 5.17, which was a major product when stoichiometric amounts of Stryker’s reagent was employed. When 5.30 bearing both a saturated and unsaturated thioester was reduced under these conditions, only the enethioate functional group underwent reaction to yield the mono-reduced product 5.31 while the saturated thioester functional group remained inert. The desymmetrizing reductive aldol reactions of symmetrical keto-enethioates 6.19, 6.22, 6.24 and 6.26 catalyzed by in situ generated chiral copper hydride were investigated. After a screening of the reaction conditions, TaniaPhos L8 was found to be the most effective chiral ligand to achieve high ee and yields. Under the optimum reaction condition (5 mol% Cu(OAc)-H2O and L8 with 2.0 eq. PhSiH3), a range of keto-enethioates smoothly underwent desymmetrizing reductive aldol cyclizations, offering bicyclic or polycyclic β-hydroxythioesters (6.28a-6.32a, 6.37a-6.47a) in 35- 84% yield and 30-97% ee with high diastereoselectivity. The addition of 5 mol% of bipyridine as additive resulted in an accelerated reaction rate in all of the reductions of keto-enethioates. The crystal structure of the L8-copper bromide complex allowed the rationalization of the major enantiomer (eg. 6.48a), in which all of the substituents are cis, to be a result of a reductively generated (Z)-thioester enolate reacting through a Zimmerman-Traxler transition state. This stereochemical outcome is in contrast to the reduction of the analogous oxoesters, which yield trans β-hydroxyesters, (eg. 6.54b), as the major products. Several proposals to explain the divergent stereochemistry, including the predominance of a Zimmerman-Traxler transition state of (E)-enolates or subsequent retroaldol rearrangements, were discussed. The retroaldol rearrangement has been observed in the conversion of 6.48a to 6.57c, in which there was retention of the configuration at C5 and a perfect conservation of enantiomeric purity. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
218

Organocatalytic asymmetric synthesis of dihydrodibenzofurans and asymmetric aziridination of α-nitroalkenes

Wang, Ziyu, 汪子玉 January 2012 (has links)
The synthesis of useful chiral skeletons from simple achiral starting materials is always the dream of organic chemists. In the past decades, organocatalysis has been rapidly developed and has become one of the most important methods in asymmetric catalysis. The aim of this thesis is to develop asymmetric methods for the construction of useful chiral skeletons based on organocatalytic chemistry. Many natural products and biologically important compounds contain the hydrogenated dibenzofuran (Figure 1) as a common sub-structure. In the first part of this thesis, the first amine-catalysed asymmetric synthesis of a dihydrodibenzofuran species from bisenal substrates has been demonstrated. After a systematic screening of various reaction parameters, the optimal conditions have been found to be as follows: 0.1 M of substrate in solution with toluene with 0.2 equiv of (S)-di(2-naphthyl)pyrrolinol TMS ether (C2.8) and 0.2 equiv of 2-nitrobenzoic acid at 50 ℃ for 7 h under an argon atmosphere (Scheme 1). The first step product, an aldehyde, can be reduced in one pot to an alcohol by NaBH4. This two-step protocol gives exclusive cis selectivity. Many chiral cis-dihydrodibenzofuran species have been synthesized from the corresponding bisenal substrates in moderate to good yield with good to excellent ee (Scheme 1). The resulting cis-dihydrodibenzofuran species have promising synthetic applications. As shown in Scheme 2, the less hindered face of the newly formed C ring is more reactive and highly regioselective functionalizations of the C ring have been achieved. In the second part of this thesis, the first asymmetric aziridination of trans-α-nitroalkenes via a phase-transfer catalysis strategy has been systematically studied. The chiral phase-transfer catalysts screened are derivatives of the cinchona alkaloids. The new cinchonidine-derived phase-transfer catalyst CD17 has been found to be optimal for the aziridination (Figure 2). Addition of a small amount of water is crucial to achieve complete conversion of the reaction. Both trans-1-nitro-2-arylalkenes and trans-1-nitro-2-alkylalkenes are suitable substrates (Scheme 3). The reaction can be run on the gram-scale without significant loss of efficiency and ee. Mechanistic studies have revealed that the aziridination proceeds through an aza-Michael addition followed by an intramolecular SN 2 type three-membered ring formation (Scheme 4). / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
219

Chiral phosphonium ion tagged and spiroindane-based organocatalysts

Hermeke, Julia January 2011 (has links)
The research on asymmetric organocatalysis has been intensifying since the beginning of 2000. The growing interest in this research area is driven by the importance of the chemical synthesis of enantiomerically pure products. While the general field of asymmetric organocatalysis has been explored intensively, the recyclability of organocatalysts has not really been considered. The attachment of phosphonium ion phase tags to chiral binaphthyl-based phosphoric acid catalyst and the use of these materials in a range of organocatalytic asymmetric Friedel-Crafts reactions of indoles have been studied. Placement of tags at the 3 and 3’ positions of the binaphthyl core, so that they could serve as steric blocking groups, failed to produce an active catalyst. However, moving the phosphonium ion groups to the 6 and 6’ positions produced an efficient and enantioselective catalyst. Aided by the presence of the phase tags, the chiral catalyst was easily recovered at the end of the reactions, and could be reused several times, albeit with somewhat decreased efficiency and enantioselectivity. Furthermore, the synthesis of 1,1’-spirobiindane-7,7’-diol and their spiroindane-based derivatives have been explored. The (R)-1,1’-spirobiindane- 7,7’-diamine was successfully applied in exo selective asymmetric Diels-Alder reactions of -unsaturated aldehyde with cyclopentadiene. However, moderate results aspire further studies in assay of (R)-1,1’-spirobiindane-7,7’-diamine derivatives, which bear various bulky groups at the 6 and 6’ positions. Moreover, the conversion of the SPINOL into a spiroindane ketone unfortunately failed, which was caused by the sterically crowded structure of the SPINOL skeleton. / published_or_final_version / Chemistry / Master / Master of Philosophy
220

Development of hydrogen-mediated carbon-carbon bond formations

Jang, Hye-Young 28 August 2008 (has links)
Not available / text

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