Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Paul Hsiao-tseng Liang. / Ph.D.

Thesis. 1978. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemistry. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / Ph.D.

Chen Ji = 由純淨有機物質及其混合物產生的具有退極化性質的超瑞利散射的光譜研究 / 陳佶. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (leaves 91-92). / Text in English; abstracts in English and Chinese. / Chen Ji = You chun jing you ji wu zhi ji qi hun he wu chan sheng de ju you tui ji hua xing zhi de chao Ruili san she de guang pu yan jiu / Chen Ji. / Abstract --- p.i / Chhiese Abstract --- p.ii / Acknowledgments --- p.iii / Table of Contents --- p.iv / List of Figures and Tables --- p.vii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Basic Theory --- p.5 / Chapter 2.1 --- A brief introduction to nonlinear optics --- p.5 / Chapter 2.2 --- Second Harmonic Generation (SHG) --- p.7 / Chapter 2.3 --- Hyper Rayleigh Scattering (HRS) --- p.9 / Chapter 2.4 --- Comparison between Second Harmonic Generation and Hyper Rayleigh Scattering --- p.10 / Chapter 2.5 --- HRS signal from a liquid --- p.12 / Chapter 2.6 --- Methods for measuring hyperpolarizability βby HRS --- p.13 / Chapter 2.7 --- Theoretical description of the depolarization ratio in HRS for a rod-like molecule --- p.16 / Chapter 2.8 --- Organic molecules with strong quadratic nonlinearities --- p.20 / Chapter Chapter 3 --- Experimental Setup --- p.25 / Chapter 3.1 --- Introduction --- p.25 / Chapter 3.2 --- Detailed descriptions of the main componets --- p.27 / Chapter 3.2.1 --- Laser system --- p.27 / Chapter 3.2.2 --- Scattered light collection system --- p.29 / Chapter 3.2.3 --- Data acquisition system --- p.32 / Chapter 3.3 --- Basic performance tests of the experimental setup --- p.35 / Chapter 3.3.1 --- Temporal stability of the apparatus --- p.35 / Chapter 3.3.2 --- Linearity of the light detection apparatus --- p.36 / Chapter 3.3.3 --- Background noise --- p.38 / Chapter 3.4 --- Sample preparation --- p.40 / Chapter Chapter 4 --- General spectral measurements and measurement of hyperpolarizability β for some organic chemicals --- p.41 / Chapter 4.1 --- Low and high resolution HRS spectra of several common liquids --- p.41 / Chapter 4.2 --- Experimental performance test of HRS by using PNA solution --- p.45 / Chapter 4.3 --- Measurements of the first order hyperpolarizability b for Crystal Violet (CV) by a modified Internal Reference Method (IRM) --- p.50 / Chapter 4.3.1 --- Basic spectral measurement of CV --- p.50 / Chapter 4.3.2 --- Measurement of hyperpolarizability β for CV --- p.52 / Chapter Chapter 5 --- Study of coherent and incoherent hyper-Rayleigh scattering for organic chemicals --- p.57 / Chapter 5.1 --- Introduction --- p.57 / Chapter 5.2 --- Calibration of the experimental setup --- p.59 / Chapter 5.3 --- "Study of depolarization ratio of PNA solution, Nitrobenzene and CCl4" --- p.64 / Chapter 5.4 --- Further study of depolarization ratio for Nitrobenzene and its mixtures --- p.68 / Chapter 5.5 --- More studies on depolarization ratios for CC14 and Nitrobenzene --- p.79 / Chapter 5.6 --- "Spectral study of PNA solution, Nitrobenzene and its mixtures" --- p.83 / Chapter 5.7 --- Summary --- p.85 / Chapter Chapter 6 --- Conclusions --- p.88 / References --- p.91

Su Pak Lee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 79-84). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgement --- p.iii / Abstract --- p.iv / Abbreviation --- p.vi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- Stoichiometric Oxidant --- p.4 / Chapter 1.2.1 --- Chromium Trioxide-pyridine --- p.5 / Chapter 1.2.2 --- "Chromium Trioxide-3,5-dimethylpyrazole" --- p.6 / Chapter 1.3 --- Catalytic Allylic Oxidation --- p.8 / Chapter 1.3.1 --- Homogeneous Catalysts --- p.8 / Chapter 1.3.1.1 --- Chromium Catalysts --- p.8 / Chapter 1.3.1.2 --- Iron Catalysts --- p.11 / Chapter 1.3.1.3 --- Copper Catalysts --- p.13 / Chapter 1.3.1.4 --- Palladium Catalysts --- p.14 / Chapter 1.3.1.5 --- Rhodium Catalysts --- p.19 / Chapter 1.3.2 --- Heterogeneous Catalysts --- p.22 / Chapter 1.4 --- Manganese(III) Acetate --- p.24 / Chapter 1.5 --- General Application of Manganese(III) Acetate --- p.25 / Chapter 1.5.1 --- Oxidative Free Radical Cyclization --- p.25 / Chapter 1.5.2 --- α-Acetoxylation --- p.27 / Chapter 1.6 --- Manganese(III) Catalyzed Reactions --- p.28 / Chapter 1.6.1 --- Epoxidation --- p.28 / Chapter 1.6.2 --- Sulfur oxidation --- p.29 / Chapter 2. --- Results and Discussions --- p.31 / Chapter 2.1 --- The Scope --- p.31 / Chapter 2.2 --- Tuning of Reaction Conditions --- p.32 / Chapter 2.2.1 --- Variation of Oxidant --- p.32 / Chapter 2.2.2 --- Variation of the Amount of Oxidant and Catalyst --- p.34 / Chapter 2.2.3 --- Variation of Solvent --- p.36 / Chapter 2.3 --- Results of Allylic Oxidation under Optimized Conditions --- p.39 / Chapter 2.4 --- Modification of Manganese(III) Acetate Catalysed Allylic Oxidation --- p.46 / Chapter 2.4.1 --- By Adding Base --- p.46 / Chapter 2.4.2 --- Assistance by Oxygen --- p.49 / Chapter 2.5 --- Mechanism --- p.53 / Chapter 3. --- Conclusion --- p.60 / Chapter 4. --- Experimental Section --- p.62 / Chapter 5. --- References --- p.79 / Chapter 6. --- Appendix --- p.85

Chapter 1 presents an overview of the lanthanide chemistry with cyclopentadienyl and cyclopentadienyl-free ligands. The chemistry of divalent lanthanide is also briefly reviewed. / Chapter 2 describes the preparation and characterization of a series of lanthanide(III) amides derived from the bidentate 2-pyridyl amido ligand [N(SiMe3)(2-C5H3 N-6-Me)] (L 1): [Ln(L1)3] [L1=, Ln = Yb (7), Sm (8), Dy (9)], [Ln(L 1)3(THF)] [Ln = Pr (10), Gd (11)], and [(L1)2Ln(mu-OBut) 2Li(THF)x] (x = 2, Ln = Nd (12), Sm ( 13), Eu (14); x = 1, Ln = Dy (15), Er ( 16)). / Chapter 3 describes the preparation and characterization of divalent lanthanide amides derived from L1 and the more bulky [N(SiButMe2)(2-C5H 3 N-6-Me)] (L2) ligands, namely [Ln(Ln) 2(tmeda)] (n = 1, Ln = Yb (17), Eu (20); n = 2, Ln = Yb (18)), [(L1)3YbK(THF)] (19), and [(L2)3EuK(tmeda)] ( 21). Complexes 17-21 were prepared by direction reaction of LnI2(THF)), (Ln = Eu or Yb) with the potassium salts of L 1 and L2. Attempts to synthesize the analogous Sm(II) and Dy(II) derivatives were unsuccessful. The divalent samarocene, [(C 5H3(SiMe3)2)2Sm(THF)] ( 24), was also prepared in our work. Subsequent reaction of 24 with 1,3-dicyclocarbodiimide (DCC) in THF yielded the dinuclear Sm(III) bisamidinate compound [(Cp")2Sm(NC6H11) 2CC(H11C6N)2Sm(Cp")2] ( 25). / Chapter 4 describes the preparation and characterization of divalent Sm, Eu and Yb complexes derived from the bulky dianionic [R 2Si(NC6H3Pri2-2,6) 2]2- (R = Me or Ph) ligands. Treatment of LnI2(THF)), (Ln = Sm, Eu, and Yb) with K2(Ln)(THF) x (L3 = Me2Si(NC6H3Pr i2-2,6)2, L4 = Ph2Si(NC 6H3Pri2-2,6)2) afforded the corresponding Ln(II) derivatives, [(L4)2Sm{K(OEt 2)}2] (36), [(C)2Ln {K(THF) 2}2] (n = 4, Ln = Yb (39); n = 3, Ln = Sm ( 37), Yb (40), Eu (44), and the mononuclear compound [(L4)Yb(THF)3] (38). / However, attempts to prepare divalent Nd and Dy complexes of the dianionic ligands were unsuccessful. Only the corresponding Nd(III) and Dy(III) complexes were isolated. In our studies, five lanthanide(III) complexes, namely [{K(THF) 6}Ln(L4)2] (Ln = Sm (34), Yb (41), Nd (42), Dy (43)) and [(L 3)2SmK(THF)3] (35) were isolated. / This thesis describes the synthetic and structural studies of lanthanide complexes derived from the monoanionic 2-pyridyl amido ligands [N(R)(2-C 5H3N-6-Me)]- (R = SiMe3, SiBu tMe2), the dianionic [R2Si(NC 6H3 Pri2-2,O2] 2- (R = Me or Ph) ligands, and the bis(trimethylsilyl)-cyclopentadienyl [C5H3(SiMe3)2]- ligand. / Pan, Chengling. / "February 2008." / Source: Dissertation Abstracts International, Volume: 70-03, Section: B, page: 1665. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Several series of amphiphilic dendritic organocatalysts 100--112 containing an optically active, polar proline-derived core, bearing [G1]--[G3] nonpolar hydrocarbon dendrons were synthesized by a convergent approach. These compounds were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and size exclusion chromatographic analysis. Such proline-based organocatalysts have been found to give products in high enantioselectivities in asymmetric aldol reactions and Michael additions in emulsion systems. The incorporation of hydrophobic dendrons in our catalyst has the advantages of promoting emulsion formation in water, enhancing the reactivity and selectivity of the asymmetric reactions, and facilitating catalyst recovery after the reactions. / This thesis describes the syntheses of chiral amphiphilic dendritic organocatalysts and their catalytic applications in asymmetric aldol reactions, Michael additions, and Mannich reactions. / Lo, Chui Man. / Adviser: Hak-Fun Chow. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3511. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 158-179). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

An enone was synthesized from delta-D-gluconolactone in four steps, involving a one-pot TPAP oxidation-K2CO3-mediated intramolecular Horner-Wadsworth-Emmons (HWE) olefination as the key step. / In this thesis, a review regarding intramolecular direct aldol reaction from 1971 to 2008 is presented. The background information on pseudo-acarviosin, valiolamine and its containing compounds, gabosines and human glutathione transferase (hGST) is introduced. / Intramolecular direct aldol reaction was investigated for the construction of cyclohexanones and cycloheptanones from carbohydrates. Amine bases, amide bases and L-proline were employed to facilitate cyclization of 1,5- and 1,6-diketones successfully. These 1,5- and 1,6-diketones were prepared from carbohydrates by standard transformations. Different bases were employed to promote cyclization of 1,5-diketone derived from D-glucose to give cyclohexanones stereoselectively. / Intramolecular nitrile oxide-alkene cycloaddition (INOC) was studied with sugar derivatives having free hydroxyl groups. The INOC reaction, by incorporating chloramine-T and silica gel for the formation of nitrile oxide from oxime, proceeded smoothly with one, two, and four unmasked hydroxyl groups to give cyclopentanes and cyclohexanes. / The polyhydroxylated carbocycles constructed from sugars were successfully transformed into a variety of target molecules including pseudo-acarviosin, valiolamine and its containing compounds and gabosines. A series of 2-crotonyloxymethyl-(4 R,5R,6R)-4,5,6-trihydroxy-2-cyclohexenone (COTC) analogues as inhibitors of hGST were prepared in order to study the structure-activity relationships. / Cheng, Hau Man. / Adviser: Tony K. M. Shing. / Source: Dissertation Abstracts International, Volume: 70-06, Section: B, page: 3508. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 214-224). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

*Please refer to dissertation for diagrams. / In Chapter 2, the development of organocatalysis is briefly summarized. Also the development of asymmetric Morita-Baylis-Hillman (MBH) reaction and asymmetric Diels-Alder (DA) reaction and their strategies are presented. Some representative examples are delineated with in-depth discussion. / In Chapter 3, the idea of the design of organocatalysts from tetraphenylenes is illustrated. The syntheses of enantiopure (S,S)- and ( R,R)-1,8,9,16-tetrahydroxytetraphenylene (1) and racemic 1,4,5,8,9,16-hexahydroxytetraphenylene (2) are described. The functionalization of compounds 1 and 2 and the attempt to synthesize amino acid from compound 1 are discussed. The syntheses of racemic and chiral amine derivatives from compound 1 and their applications on the catalysis of MBH reaction and asymmetric DA reaction are presented and discussed. / In Chapter 4, the application of marcocyclic compounds on enantiomeric recognition is briefly reviewed. The strategies and syntheses of the two enantiomeric tetrameric form of 1,8,9,16-tetraalkoxytetraphenylene, which is a potential chiral recognition reagent, are discussed. / In Chapter 5, the background information of the chemistry of liquid crystals is briefly reviewed, and the syntheses of different alkoxy-derivatives from compound 1 are presented. Among these derivatives, three of them were found to have liquid crystal properties. The details on the characterization of their liquid crystal properties are discussed. / In Chapter 6, a short summary and conclusion of the results in the previous chapters are given. / In Chapter 7, experimental details are summarized.* / Tetraphenylenes are structurally exceptional molecules featuring a rigid conformation. As such, substituents of these compounds would demonstrate highly directional disposition. As a result, these molecules, in their optically pure forms, are potential candidates as organocatalysts in asymmetric synthesis. In this thesis, some essential background information and previous works about the development of the tetraphenylenes are first presented in Chapter 1. / The second part is about the potential applications of tetraalkoxytetraphenylene derivatives. / The thesis is divided into two parts. The first part is about the applications of amino-substituted tetraphenylene derivatives as organocatalysts. / pt. 1. Amino-substituted tetraphenylene derivatives as organocatalysts -- pt. 2. Potential applications of tetraalkoxytetraphenylenes. / Hau, Chun Kit. / Adviser: H. N. C. Wong. / Source: Dissertation Abstracts International, Volume: 72-04, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 260-282). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

by Zhang Lirong. / "September 2006." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

by Yip Ting. / Thesis submitted in 1997. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (leaves 55-59). / Abstract also in Chinese. / Acknowledgment --- p.i / Table of Contents --- p.ii / Abstract --- p.iii / Abbreviation --- p.iv / Chapter Part 1 --- Introduction --- p.1 / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- Review on the Published Syntheses of Zoapatanol --- p.2 / Chapter Part 2 --- Results and Discussion --- p.12 / Chapter 2.1 --- Synthetic Strategy --- p.12 / Chapter 2.1.1 --- Synthesis of Tertiary Alcohol46 --- p.14 / Chapter 2.1.2 --- Synthesis of Vinyl Bromide 55-Z --- p.15 / Chapter 2.1.3 --- Synthetic studies on39 --- p.18 / Chapter 2.1.4 --- Synthetic studies on40 --- p.19 / Chapter 2.2 --- Synthetic Strategy --- p.23 / Chapter 2.2.1 --- Synthesis of 79 - route1 --- p.24 / Chapter 2.2.2 --- Synthesis of 79 - route2 --- p.26 / Chapter 2.2.3 --- Synthesis of 79 - route3 --- p.28 / Chapter 2.2.4 --- Synthetic studies on free radical cyclization of79 --- p.30 / Chapter 2.2.5 --- Synthesis of83 --- p.31 / Chapter 2.2.6 --- Synthetic studies on carbanion cyclization of83 --- p.31 / Chapter Part 3 --- Conclusion --- p.33 / Chapter Part 4 --- Experimental --- p.34 / Chapter Part 5 --- References --- p.55