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The work in this thesis describes investigations into the development of a tandem radicallDiels-Alder reaction strategy for the construction of indole alkaloids. The synthesis of a key precursor, 2-[(4-methylphenyl)sulfonyl]indole, was investigated and involved two main· strategies: functionalisation of the indole ring using lithiation procedures and assembling the indole as a key step (chapter 2). A method based on the former strategy was deemed to be the most practical and delivered the desired product in moderate yields (35 - 45%). The viability of the first step of the proposed tandem radicallDiels-Alder strategy was investigated by examining the intramolecular addition of vinyl and aryl radicals to a sulfone substituted indole (chapter 3). These studies showed that the addition of sp2 centred radicals to substituted indoles was feasible (20 - 40%). A study using an acetylenic precursor also provided useful information about the relative rates of desulfonylation and radical addition to acetyleneS; de-sulfonylation is a competing process. An alternative tandem palladiumlDiels-Alder reaction was briefly examined, but was thwarted by capricious palladium catalysed cross coupling reactions. Further studies were carried out to extend the scope of the novel ipso substitution reaction (chapter 4). It was found that alkyl radical cyclisations proceed efficiently to give a new ~ethod for the synthesis of fused[1,2-a]indoles (30 - 84%). The feasibility of a related ipso substitution using phenylthio and phenylsulfinyl substituted indoles was also examined. It was found that these reactions are also successful, but proceed in reduced yields compared with the sulfones (24 - 51 %). These results could be attributed to the more favoured reaction of the electron rich carbon centred radical with the more electrophilic 1t bond. The thesis is concluded by a brief discussion of the mechanism of these cyclisations with the available experimental evidence supporting an addition! elimination pathway.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Science

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

四苯並環辛四烯是具有獨特結構而令人感興趣的分子。手性的四苯並環辛四烯可能呈現出特別的性質。本文第一章綜述了一些關於四苯並環辛四烯的基本資訊和研究進展。 / 第二章簡要介紹了合成手性四苯並環辛四烯的幾種方法。文中闡述了合成具有光學活性的四羥基四苯並環辛四烯(R,R)-60 和(S,S)-60的策略和合成方法。 / 第三章敘述了冠醚及其衍生物對手性銨離子識別的相關研究進展。同時， 對設計和合成四苯並環辛四烯四聚化合物、五聚化合物、六聚化合物進行了詳細討論。通過使用紫外滴定實驗，本章還研究了這些合成的受體對於手性氨基酸甲酯鹽的對映選擇性。 / 第四章，簡要綜述了冠醚與富勒烯之間識別的化學研究進展。本章同時描述了羥基大環冠醚、四聚體(R,R,S,S,R,R,S,S)-122以及四聚體的二聚體的合成策略和方法。文中從理論計算和實驗研究分別討論了這些受體和富勒烯之間相互作用。 / 第五章是總結與結論。 / 第六章是實驗部分[附圖]。 / Tetraphenylene is a structurally highly intriguing molecule. Chiral version of tetraphenylenes would exhibit special properties. In this thesis, some fundamental information and the developmental works on tetraphenylenes are described in Chapter I. / In Chapter II, various methods on synthesis of chiral tetraphenylene are briefly summarized. The strategies and syntheses of optically pure tetrahydroxytetraphenylenes (R,R)-60 and (S,S)-60 are presented. / In Chapter III, examples on crown ethers and their derivatives on chiral recognition towards ammonium ions are discussed. Also the design and syntheses of chiral marcrocyclic ethers such as tetramer, pentamer and hexamer are illustrated. Enantiomeric recognition of the hosts prepared towards amino acid methyl ester salts was investigated by using UV spectroscopic titration. / In Chapter IV, background on the chemistry of crown ether for recognition fullerenes is briefly reviewed. The syntheses of potential hydroxy macrocyclic crown ethers, tetramer (R,R,S,S,R,R,S,S)-122 together with tetramer dimer are demonstrated. The theoretically calculation and experimental results on these prepared potential hosts to recognize fullerenes are discussed. / In Chapter V, a short summary and conclusion of the results in the previous chapters are given. / In Chapter VI, experimental details are given [With images]. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Cheng, Chao. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references (leaves 173-182). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts also in Chinese. / Acknowledegements --- p.I / Abstract --- p.III / Abstract (Chinese Version) --- p.V / Abbreviation --- p.VII / Chapter Chapter I --- Introduction --- p.1 / Chapter 1.1 --- Background of Tetraphenylenes --- p.1 / Chapter 1.2 --- The Methods for Preparation of Tetraphenylenes --- p.3 / Chapter 1.2.1 --- Lithiation With Metal Assisted Coupling Reaction --- p.4 / Chapter 1.2.2 --- High Temperature Pyrolysis --- p.4 / Chapter 1.2.3 --- Diels-Alder Cycloaddition With Subsequent Dehydrogenation --- p.5 / Chapter 1.3 --- Synthesis of Substituted Tetraphenylenes --- p.6 / Chapter 1.3.1 --- Electrophilic Aromatic Substitution of Tetraphenylenes --- p.6 / Chapter 1.3.2 --- Metal Catalysis at High Temperature --- p.8 / Chapter 1.3.4 --- [2+2+2] Cycloaddition-Based Strategy --- p.11 / Chapter 1.3.5 --- Benzo-Fused Tetraphenylenes from Diels-Alder Cycloaddition and Deoxygenation Protocol --- p.12 / Chapter 1.4 --- Applications of Tetraphenylene Derivatives as New Materials and Catalysts --- p.13 / Chapter 1.4.1 --- Applications of Tetraphenylene Derivatives as Molecular Devices --- p.14 / Chapter 1.4.2 --- Applications of Tetraphenylene Derivatives as Liquid Crystals --- p.16 / Chapter 1.4.3 --- Applications of Tetraphenylene Derivatives as Supramolecular Scaffolds --- p.17 / Chapter 1.4.4 --- Applications of Tetraphenylene Derivatives in Asymmetric Catalytic Reaction --- p.21 / Chapter Chapter II --- Asymmetric Synthesis of Chiral Tetraphenylenes --- p.24 / Chapter 2.1 --- Brief Introduction of Hydroxytetraphenylenes --- p.24 / Chapter 2.2 --- Synthesis of Chiral Substituted Tetraphenylenes --- p.25 / Chapter 2.2.1 --- Lithiation with Metal Assisted Coupling Reaction --- p.25 / Chapter 2.2.2 --- Ligand Induced Coupling Reaction --- p.26 / Chapter 2.2.3 --- Rhodium Catalyzed [2+2+2] Cycloaddition --- p.27 / Chapter 2.2.4 --- Resolution of Racemic Substituted Tetraphenylenes --- p.28 / Chapter 2.3 --- Project Aim --- p.29 / Chapter 2.4 --- Results and Discussion --- p.30 / Chapter 2.4.1 --- Design of Chiral Tetraphenylenes --- p.30 / Chapter 2.4.2 --- Synthesis of Chiral Hydroxylated Tetraphenylenes --- p.33 / Chapter Chapter III --- Design and Synthesis of Chiral Marcrocyclic Derivatives of Tetraphenylene for Enantiomeric Recognition of Chiral Amino Acids --- p.45 / Chapter 3.1 --- Brief Introduction of Molecular Recognition --- p.45 / Chapter 3.2 --- Examples of Crown Ether Recognition Ammonium Salts --- p.46 / Chapter 3.3 --- Project Aim --- p.54 / Chapter 3.4 --- Results and Discussion --- p.54 / Chapter 3.4.1 --- Design of Macrocyclic Crown Ethers as Receptors --- p.54 / Chapter 3.4.2 --- Synthesis of Chiral Macrocyclic Crown Ethers --- p.59 / Chapter 3.4.3 --- Enantiomeric Recognition Studies Using UV-Titration Method --- p.72 / Chapter Chapter IV --- Potential Applications as Receptors of Fullerenes --- p.88 / Chapter 4.1 --- Background on the Chemistry of Crown Ether for Recognition of Fullerenes --- p.88 / Chapter 4.2 --- Project Aim --- p.96 / Chapter 4.3 --- Results and Discussion --- p.96 / Chapter 4.3.1 --- Design New Potential Candidates --- p.96 / Chapter 4.3.2 --- Calculation Results --- p.98 / Chapter 4.3.3 --- Synthesis of Potential Hosts --- p.102 / Chapter 4.3.4 --- Experimental Results --- p.112 / Chapter Chapter V --- Summary and Conclusion --- p.115 / Chapter Chapter VI --- Experimental Sections --- p.120 / References --- p.173 / Appendix --- p.183

by Chun Wing Lai. / Thesis submitted in: August 2002. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 87-92). / Abstracts in English and Chinese. / ACKNOWLEDMENTS --- p.1 / CONTENTS --- p.2 / ABTRACT --- p.5 / Chapter CHAPTER 1 --- INTRODUCTION --- p.7 / Chapter 1.1 --- General background --- p.7 / Chapter 1.2 --- Synthesis of tetraphenylene and its derivatives --- p.8 / Chapter 1.2.1 --- From electrophililc aromatic substitution --- p.9 / Chapter 1.2.2 --- From biphenylene pyrolysis --- p.10 / Chapter 1.2.3 --- From aryl halide coupling --- p.13 / Chapter 1.2.4 --- From bis-acetylene --- p.15 / Chapter 1.2.5 --- Synthesis of tetraphenylenes fused with carbocycles and heterocycles --- p.17 / Chapter 1.3 --- Inversion barrier of tetraphenylenes --- p.21 / Chapter 1.4 --- Clathrate inclusion properties of tetraphenylene and its derivatives --- p.27 / Chapter 1.5 --- Tetraphenylenols --- p.33 / Chapter CHAPTER 2 --- RESULTS AND DISCUSSION / Chapter 2.1 --- Aim of the present work --- p.38 / Chapter 2.2 --- "Retrosynthetic studies on 1,4,5,8,9,12,13,16-octahydroxytetraphenylene" --- p.39 / Chapter 2.2.1 --- "1,4,5,8-tetramethoxybiphenylene approach" --- p.39 / Chapter 2.2.2 --- "2,2'-diiodo-3,3',6,6'-tetramethoxybiphenyl approach" --- p.42 / Chapter 2.3 --- "Preparation of 1,4,5,8-tetramethoxybiphenylene" --- p.44 / Chapter 2.3.1 --- "From 2-amino-3,6-dimethoxybenzoic acid" --- p.44 / Chapter 2.3.2 --- "From l-amino-4,7-dimethoxybenzotriazole" --- p.47 / Chapter 2.4 --- "Synthesis of 1,4,5,8,9,12,13,16-octamethoxytetraphenylene from 1,4,5,8-tetramethoxybiphenylene" --- p.50 / Chapter 2.5 --- "Synthesis of 2,2'-diiodo-3,3',6,6'-tetramethoxybiphenyl" --- p.51 / Chapter 2.6. --- "Synthesis of 1,4,5,8,9,12,13,16-octamethoxytetraphenylene from 2,2，-diiodo-3,3 ',6,6' -tetramethoxybiphenyl" --- p.53 / Chapter 2.7 --- Synthesis of other tetraphenylene derivatives --- p.57 / Chapter 2.8 --- X-ray crystallographic studies of tetraphenylene derivatives --- p.59 / Chapter 2.8.1 --- "X-ray crystallographic studies of 1,4,5,8,9,12,13,16-octamethoxytetraphenylene" --- p.59 / Chapter 2.8.2 --- "X-Ray crystallographic studies of 1,4,5,8,9,12,13,16-octahydroxytetraphenylene" --- p.61 / Chapter 2.9 --- "Electrochemical properties of 1,4,5,8,9,12,13,16-octamethoxytetraphenylene and l,4,5,8,9,12,13,16-octahydro-l,4,5,8,9,12,13,16-octaoxo- tetraphenylene" --- p.62 / Chapter 2.9.1 --- "Electrochemical properties of 1,4,5,8,9,12,13,16-octamethoxytetraphenylene" --- p.65 / Chapter 2.9.2 --- "Electrochemical properties of 1,4,5,8,9,12,13,16-octahydro-1,4,5,8,9,12,13,16-octaoxo- tetraphenylene" --- p.66 / Chapter CHAPTER 3 --- CONCLUSION --- p.69 / Chapter CHAPTER 4 --- EXPERIMENTAL SECTION --- p.70 / REFERENCES --- p.87 / APPENDICES --- p.93 / Chapter I. --- List of NMR spectra --- p.95 / Chapter II. --- List of cyclic voltammetric data --- p.109 / Chapter III. --- List of X-ray crystallographic data --- p.111

Yang, Bi Bo. / Thesis submitted in: October 2007. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 58-64). / Abstracts in English and Chinese. / ABSTRACT --- p.iii / ABBREVIATIONS --- p.vi / INTRODUCTION --- p.1 / Chapter 1.1 --- General background --- p.1 / Chapter 1.1.1 --- Cyclooctatetraene --- p.1 / Chapter 1.1.2 --- Benzannelated cyclooctatetraenes --- p.2 / Chapter 1.1.3 --- Cyclooctatrienyne --- p.4 / Chapter 1.1.4 --- Benzannelated cyclooctatrienynes --- p.4 / Chapter 1.2 --- "Tetrabenzo[a,c,e,g]cyclooctatetraene (tetraphenylene) (1)" --- p.7 / Chapter 1.2.1 --- Ring inversion barrier of tetraphenylenes --- p.8 / Chapter 1.2.2 --- Inclusion properties of tetraphenylenes --- p.9 / Chapter 1.3 --- Synthetic methods for tetraphenylene (1) and its derivatives --- p.10 / Chapter 1.3.1 --- Electrophilic aromatic substitution on tetraphenylenes --- p.10 / Chapter 1.3.2 --- Diels-Alder reactions of cyclooctadienediyne --- p.11 / Chapter 1.3.3 --- Pyrolysis of biphenylene --- p.12 / Chapter 1.3.4 --- Transition metal complexes-promoted ring expansion-dimerization of biphenylene --- p.13 / Chapter 1.3.5 --- "Coupling of 2,2'-dihalobiphenyls" --- p.14 / Chapter 1.4 --- Applications of tetraphenylene derivatives as functional materials --- p.17 / Chapter 1.4.1 --- Tetraphenylene derivatives employed as molecular devices --- p.17 / Chapter 1.4.2 --- Tetraphenylene derivatives employed as building blocks for liquid crystals --- p.18 / Chapter 1.5 --- Tetraphenylenols as building blocks for molecular scaffolds --- p.18 / RESULTS AND DISCUSSION --- p.23 / Chapter 2.1 --- "Synthesis of 1,4,5,16-tetrahydroxytetraphenylene (68)" --- p.23 / Chapter 2.1.1 --- "Preparation of 1,10-dimethoxydibenzo[a,e]cyclooctene (82)" --- p.25 / Chapter 2.1.2 --- "Preparation of 1,12-dimethoxytribenzo[a,c,e]cyclooctene (97)" --- p.28 / Chapter 2.1.3 --- "Preparation of 1,4-endoxo-1,4-dihydro-5,l6- dimethoxytetraphenylene (81)" --- p.31 / Chapter 2.1.4 --- "Preparation of 1,4,5,16-tetrahydroxytetraphenylene (68)" --- p.33 / Chapter 2.2 --- Molecular scaffold consisting of tetraphenylenol 68 and (S)-(BINAP)PtC03 --- p.36 / Chapter 2.3 --- "Preparation of 1,4,5,16-tetracyanotetraphenylene (77)" --- p.37 / CONCLUSION --- p.40 / EXPERIMENTAL --- p.41 / REFERENCES --- p.58 / APPENDICES --- p.65

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.