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Thesis (M. Sc.)--University of Hong Kong, 1966. / Typewritten.

This thesis focuses on the construction of individual isomers of the R-CHF-CHF-CHF-R’ motif. The multi-vicinal fluorine motif is new in organic chemistry and therefore stereoselective methods giving rapid access to these motifs and with flexibility need to be explored. The research in the thesis succeeded in the preparation of (2S,3R,4S)-314 and (2S,3S,4R)-328. In Chapter 1, an overview of the impact of fluorine in organic molecules is given. Recent developments in asymmetric electrophilic and nucleophilic fluorination are described, as well as the preparation of multivicinal fluoroalkane motifs. Aldol reactions of either (R)- or (S)-N-(α-fluoropropyl)-2-oxazolidinones, mediated by TiCl 4 are reported in Chapter 2. Such aldol reactions gave rise to identical α-fluoro-β-hydroxy- aldol products with high diastereoselectivities (95% dr). After removal from the auxiliary α- fluoro-β-hydroxy- products were converted to the corresponding α,β-difluoro products. The synthesis of non symmetric vicinal trifluoro motifs (2S,3R,4S)-314 and (2S,3S,4R)-328 is described in Chapter 3. They were prepared by direct fluorination in three steps of the corresponding (2R,3R,4R)-erythro and (2R,3S,4S)-threo enantio-enriched epoxy-alcohols. The two erythro and threo epoxy-alcohol isomers behave very differently during the first fluorination step and then an attempt to study and rationalise this difference in behaviour is made.

Thesis (Ph.D.) - University of St Andrews, June 2008.

Organofluorine compounds find various applications ranging from pharmaceuticals to refrigerants, insecticides, high-value fluoropolymers and reagents in catalysis. However, the synthesis of organofluorine compounds depends on toxic chemicals such as hydrogen fluoride, chlorinated hydrocarbons, reactive F2 gas and environmentally persistent long-chain fluorosurfactants. Recently more sustainable, energy-efficient syntheses have been developed using base metal-catalyzed transformations of fluoroalkenes and the formation and functionalization of d6-8 fluorometallacycles. In this thesis, we use manganese complex precursors to prepare the first examples of d4 fluorometallacycles. Work in Chapter 2 describes the synthesis and one-electron reduction of manganese bis(diphosphine)- and tetrakis(phosphite) dibromide complexes, MnBr2(P-P)2 and MnBr2[P(O-i-Pr)3]4 and reactions of the corresponding reduced Mn(I)Br complexes with tetrafluoroethylene (TFE). Products proposed to be d4 perfluorometallacycles, MnBr[-CF2(CF2)2CF2-](P-P) proved to be unstable, reforming TFE upon application of vacuum. In Chapter 3 we show that photolysis of ligated manganese(I) carbonyl bromide complexes, MnBrLn(CO)5-n, in the presence of TFE, chlorotrifluoroethylene (CTFE) or perfluoro(methyl vinyl ether) (PMVE) in tetrahydrofuran affords the Mn-H insertion products, Mn(CF2CFXH)(L2)(CO)3 (X = F, Cl, OCF3) only for L2 = DPPE [1,2-bis(diphenylphosphino)ethane] as well as a solid by-product proposed to be MnBr2Ln. These reactions are accompanied by THF fluoroalkylation products, O[-(CH2)3CH(CF2CFHX)-]. By switching to methyl t-butyl ether solvent, we showed that exhaustive photolysis of MnBr(CO)5 + 3 equiv. of DPPE gave a new product proposed to be the first stable d4 fluorometallacycle, MnBr[-(CF2)4-](CO)(DPPE). Reactions of the fluoroalkenes with zerovalent Mn2(CO)10 also contributed to our understanding of potential reaction pathways to form these Mn-H-derived products. Previous work in the Baker group compared FeH2(dmpe)2 and [FeH(H2)(dmpe)2]+ as catalysts for the dehydrogenation of amine-boranes [dmpe = 1,2-bis(dimethylphosphino)ethane]. In Chapter 4 the catalytic reactivity and selectivity of MnH(H2)(dmpe)2 are compared with those observed using the Fe analogs and the catalyst resting state, Mn(2-BH4)(dmpe)2, is identified. Finally, in Chapter 5 we summarize the findings of this thesis and suggests future directions based on this work.

No description available.

M.S.

No description available.

This thesis focuses on studies investigating the structure of intermediates involved in fluorometabolite biosynthesis, and the potential applications of the fluorinase enzyme in positron emission tomography (PET). Chapter 1 introduces the rare natural occurrence of fluorinated compounds. The bacterium Streptomyces cattleya is known to biosynthesise two fluorinated secondary metabolites: the toxin fluoroacetate (FAc) and the antibiotic 4-fluorothreonine (4-FT). The enzymes and intermediates identified on this fluorometabolite biosynthetic pathway in S. cattleya, prior to this research, are discussed in detail. Chapter 2 presents studies towards the unambiguous structural identification of (3R,4S)-5- deoxy-5-fluoro-D-ribulose-1-phosphate (5-FRulP) as the third fluorinated intermediate on the biosynthetic pathway to fluoroacetate and 4-fluorothreonine in S. cattleya. Chapter 3 describes the synthetic routes to key molecules, necessary as reference compounds and substrates, to underpin the subsequent studies in this thesis. In particular, synthetic routes to 5'-deoxy-5'-fluoroadenosine (5'-FDA), 5'-deoxy-5'-fluoroinosine (5'-FDI), 5-deoxy-5-fluoro-D-ribose (5-FDR) and 5-deoxy-5-fluoro-D-xylose (5-FDX) are described. Chapter 4 describes the use of the fluorinase enzyme from S. cattleya as a tool for the synthesis of new [¹⁸F]-labelled sugars with potential application in positron emission tomography (PET). A new route to 5-deoxy-5-[¹⁸F]fluoro-D-ribose ([¹⁸F]FDR) is developed in a two-step enzymatic synthesis. A total of three potential radiotracers ([¹⁸F]FDA, [¹⁸F]FDR and [¹⁸F]FDI) are synthesised using fluorinase-coupled enzyme reactions. In addition, in vitro studies are reported with these [¹⁸F]-labelled sugars to investigate their uptake and potential as PET radiotracers in cancer cells. A preliminary rat imaging study with [¹⁸F]FDA is reported. Chapter 5 details the experimental procedures for the compounds synthesised in this research and the biological procedures for chemo-enzymatic syntheses and protein purification.

Lai, Kwing To = 鐵基超導體的合成與分析 : 氟及釔合摻SmFeAsO / 黎烱韜. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Abstracts in English and Chinese. / Lai, Kwing To = Tie ji chao dao ti de he cheng yu fen xi : fu ji yi he shan SmFeAsO / Li Jiongtao. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgements --- p.v / Table of contents --- p.vii / List of table captions --- p.x / List of figure captions --- p.xi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Superconductivity --- p.1 / Chapter 1.1.1 --- Physical properties --- p.3 / Chapter 1.1.1.1 --- Zero resistance --- p.3 / Chapter 1.1.1.2 --- Meissner effect --- p.4 / Chapter 1.1.1.3 --- Josephson effect --- p.5 / Chapter 1.1.2 --- Type I and II superconductivity --- p.7 / Chapter 1.2 --- Iron-based superconductors --- p.7 / Chapter 1.2.1 --- Classifications and structures --- p.8 / Chapter 1.2.2 --- Physical properties --- p.12 / Chapter 1.2.3 --- Iron-based superconductors versus Cuprate superconductors --- p.13 / Chapter 1.2.4 --- Correlation between high-Tc superconductivity and magnetism --- p.14 / Chapter 1.2.5 --- Quantum phase transition by doping --- p.16 / Chapter 1.2.6 --- Sample preparation of undoped and doped iron-based superconductors --- p.17 / Chapter 1.3 --- Objectives of this research project --- p.18 / References --- p.20 / Chapter Chapter 2 --- Literature Review --- p.22 / Chapter 2.1 --- Theories of superconductivity --- p.22 / Chapter 2.1.1 --- London equation --- p.22 / Chapter 2.1.2 --- Ginzburg-Landau theory --- p.24 / Chapter 2.1.2.1 --- Mean-field theory and Landau theory --- p.24 / Chapter 2.1.2.2 --- Spatial varying order parameter and Gauge symmetry --- p.27 / Chapter 2.1.2.3 --- Applications --- p.31 / Chapter 2.1.3 --- BCS theory --- p.35 / Chapter 2.2 --- Magnetism in condensed matters --- p.39 / Chapter 2.2.1 --- Ferromagnetism and Antiferromagnetism from local moments --- p.40 / Chapter 2.2.1.1 --- Mathematical explanation in the mean-field approach --- p.40 / Chapter 2.2.1.2 --- Exchange interaction --- p.43 / Chapter 2.2.2 --- Antiferromagnetism in magnetic metals: Spin density wave --- p.45 / References --- p.52 / Chapter Chapter 3 --- Methodology and Instrumentation --- p.53 / Chapter 3.1 --- Sample preparation --- p.53 / Chapter 3.2 --- Characterization --- p.55 / Chapter 3.2.1 --- Scanning electron microscopy (SEM) and Energy dispersive X-ray spectroscopy (EDX) --- p.55 / Chapter 3.2.2 --- Transmission electron microscopy (TEM) and Electron diffraction --- p.55 / Chapter 3.2.3 --- X-ray diffraction (XRD) --- p.56 / Chapter 3.2.4 --- X-ray photoelectron spectroscopy (XPS) --- p.57 / Chapter 3.2.5 --- Physical properties measuring system (PPMS) --- p.58 / Chapter 3.2.5.1 --- Transport properties --- p.58 / Chapter 3.2.5.2 --- Magnetic properties --- p.60 / Chapter 3.2.6 --- Raman spectroscopy --- p.62 / Chapter 3.3 --- Precautions --- p.62 / References --- p.63 / Chapter Chapter 4 --- Results --- p.64 / Chapter 4.1 --- Fluorine-doped SmFeAsO --- p.64 / Chapter 4.1.1 --- Morphologies and microstructures --- p.67 / Chapter 4.1.2 --- Phase and composition --- p.69 / Chapter 4.1.3 --- Lattice constants --- p.72 / Chapter 4.1.4 --- Transport properties --- p.73 / Chapter 4.1.5 --- Magnetic properties --- p.74 / Chapter 4.2 --- Fluorine and Yttrium co-doped SmFeAsO --- p.78 / Chapter 4.2.1 --- Morphologies and microstructures --- p.79 / Chapter 4.2.2 --- Phase and composition --- p.82 / Chapter 4.2.3 --- Lattice constants --- p.84 / Chapter 4.2.4 --- Oxidation state --- p.85 / Chapter 4.2.5 --- Transport properties --- p.88 / Chapter 4.2.6 --- Magnetic properties --- p.89 / Chapter 4.3 --- Quality control of the superconducting products --- p.94 / Chapter 4.3.1 --- Intermediate product SmAs --- p.95 / Chapter 4.3.2 --- Intermediate product FeAs --- p.104 / Chapter 4.3.3 --- Effects of annealing temperature --- p.110 / Chapter 4.4 --- Summary --- p.112 / References --- p.112 / Chapter Chapter 5 --- Discussions --- p.113 / Chapter 5.1 --- Effects of F doping --- p.113 / Chapter 5.2 --- Effects of YF doping --- p.115 / Chapter 5.3 --- Improvements in the quality of the superconducting samples --- p.117 / Chapter 5.4 --- Summary --- p.124 / References --- p.125 / Chapter Chapter 6 --- Conclusions and Suggestions for Future work --- p.126 / Chapter 6.1 --- Conclusions --- p.'126 / Chapter 6.2 --- Suggestions for future work --- p.128 / References --- p.130 / Chapter Appendix A --- Sealing samples in small evacuated silica capsules for DTA measurements --- p.131 / Chapter Appendix B --- AC susceptibility measurement --- p.133 / Chapter Appendix C --- Suggested readings for beginners --- p.135 / Bibliography --- p.138