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Terminal 1,1-disubstituted olefins synthesis via nickel catalyzed hydroalkenylation of styrenes with α-olefins.January 2011 (has links)
He, Lisi. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 69-73). / Abstracts in English and Chinese. / Acknowledgement --- p.I / Table of Contents --- p.II / Abstract --- p.III / Abstract (Chinese Version) --- p.IV / Abbreviation --- p.V / Chapter CHAPTER 1 --- INTRODUCTION --- p.1 / Chapter 1.1 --- "Synthesis of Terminal 1,1 -Disubstituted Olefins" --- p.1 / Chapter 1.2 --- Nickel Hydride Reactions with Olefins --- p.5 / Chapter 1.3 --- Objective and Approach --- p.16 / Chapter CHAPTER 2 --- RESULTS AND DISCUSSION --- p.20 / Chapter 2.1 --- Reaction Condition Optimization --- p.20 / Chapter 2.2 --- Substrates Scope Expansion --- p.27 / Chapter 2.3 --- Examples of Post-coupling Modifications --- p.35 / Chapter 2.4 --- Application in a sp2-sp3 Heck-like Reaction --- p.38 / Chapter CHAPTER 3 --- CONCLUSION --- p.43 / APPENDIX EXPERIMENTAL --- p.46 / REFERENCE --- p.69 / GC CHROMATOGRAMS & NMR SPECTRA FOR NEW COMPOUNDS
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Some chemistry of metal alkynyls : formation of odd and even bridging carbon chainsGaudio, Maryka January 2006 (has links)
This thesis continues the study into the synthesis and analysis of metal poly - yndiyl complexes. These molecules have shown promise as model molecular wires. The study provides a general overview of the interest in carbon based molecules and introduces the need for molecular electronics. Some of the most promising classes of molecular wires are described before outlining the methods of evaluation. / Thesis (Ph.D.)--School of Chemistry and Physics, 2006.
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A synthesis of tetrahydropyrethrolone and the chemistry of ethyl diazopyruvate /Greenberg, Richard Scot, January 1983 (has links)
Thesis (Ph. D.)--University of California, San Diego, 1983. / Vita. Includes bibliographical references (leaves 101-107).
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A synthesis of tetrahydropyrethrolone and the chemistry of ethyl diazopyruvateGreenberg, Richard Scot, January 1983 (has links)
Thesis (Ph. D.)--University of California, San Diego, 1983. / Vita. Includes bibliographical references (leaves 101-107).
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Asymmetric hydrogenations of aryl alkenes using imidazol-2-ylidene iridium complexesCui, Xiuhua 29 August 2005 (has links)
A library of iridium complexes featuring oxazoline and imidazol-2-ylidene ligands
were synthesized by reaction of a library of imidazoles with a second library of oxazoline
iodides. These complexes were active catalysts for hydrogenations of aryl substituted
monoenes. Tri- and 1,1-disubstituted alkenes were hydrogenated quantitatively with ee??s
up to 99% at 1 atm hydrogen pressure. Catalyst, substrate, temperature and pressure
effects were studied.
The iridium complexes were also used for the kinetic study of hydrogenation of 2,3-
diphenylbutadiene. This hydrogenation is a stepwise reaction: one double bond was
hydrogenated first, then the second one. Both step hydrogenations were zero order in
alkene. The consumption of 2,3-diphenylbutadiene was first order in catalyst, and
probably first order in hydrogen pressure too. The enantioselectivity for the first step
hydrogenation was low. There were match and mismatch catalyst-substrate relationships
for the second step hydrogenation, and the enantioselectivities for this step were catalyst
controlled. NMR studies indicated that the initiation of the reaction involved both
hydrogen and alkene substrate. A competitive experiment was designed to explore the
formation of meso-alkane at first step hydrogenation, and the results indicated that the
alkane was formed predominantly via an associative mechanism.
Four types of conjugate dienes were synthesized and hydrogenated. Different
reactivities and selectivities were obtained for each type of dienes. In the best case, a
diene was hydrogenated quantitatively with an excellent ent/meso ratio of 20:1.0 and
99% enantioselectivity. The scope, limitation and potential applications of the reactions
were discussed. A selection of the dienes was hydrogenated with the Crabtree??s catalyst,
for comparison, and the yields, conversions and diastereoselectivities were inferior to
those from iridium-oxazoline-imidazol-2-ylidene catalysts.
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Studies on epoxidation of olefins by IN SITU generated N-sulfonyloxaziridine and ruthenium catalyzed oxidative cleavage of olefinsZhang, Chi, January 2001 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2001. / Includes bibliographical references (leaves 61-67).
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Non-heme iron(III) complexes catalyzed oxidation of saturated hydrocarbons and cis-dihydroxylation of alkenesChow, Wai-shan., 周慧珊. January 2010 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Metal complexes of porphyrins and porphycenes in catalytic cyclopropanation and aziridination of alkenes盧偉祥, Lo, Wai-cheung. January 1998 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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The cycloaddition of electron poor olefins to unsubstituted vinyl aminesGlogowski, Mark Edward, 1943- January 1976 (has links)
No description available.
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TETRAMETHYLENE INTERMEDIATES IN POLYMERIZATION AND CYCLOADDITION REACTIONSRasoul, Husam Ali Abdul January 1981 (has links)
Five tri- and tetra-substituted electron-poor olefins containing a β-leaving group, initiated cationic polymerization of p-methoxystyrene with widely varying results. As the electrophilicity of the electron-poor olefins increased, the yields and molecular weights of the polymers formed decreased. The same was true when the excellent leaving group, trifluoromethanesulfonate, was replaced by the poorer leaving group, chloride. Another series of tri-substituted olefins was prepared and reacted with p-methoxystyrene in the presence of excess methyl methacrylate or styrene. Terpolymer was formed as a major product when the electron-poor olefin used contained an α-ester group. The yield of the terpolymer increased with the increasing electrophilicity of the electron-poor olefin. The reactions of methyl α-cyanoacrylate with a number of electron-rich olefins were also studied and found to give new types of adducts, such as Diels-Alder adducts and pyrans. All these reactions were suggested to go through the formation of a tetramethylene intermediate, a resonance hybrid of a zwitterion and spin paired biradical.
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