Thesis advisor: Kian L. Tan / General and efficient methods for the selective hydroformylation of allylic alcohols and amines utilizing a directing group approach. / Thesis (MS) — Boston College, 2009. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Includes bibliographical references. / by Bruno Vincent DePamphilis. / Ph.D.

Foram medidas distribuições angulares dos canais quase-elásticos e do decaimento em fragmentos binários fortemente amortecidos dos sistemas ANTPOT. 18 O+ANTPOT. 10,11 B E ANTPOT. 28 Si + ANTPOT. 16 O em energias de E IND. LAB(ANTPOT. 18 0) = 52,5 MeV e E IND. LAB(ANTPOT. 28 0) = 107,5 e 139 MeV. Em todos os sistemas, as distribuições angulares quase-elásticas apresentam oscilações com uma subida da seção de choque em ângulos traseiros. As distribuições integradas em valor de Q, apresentam o comportamento 1/sen IND. CM em todos os sistemas indicando uma vida-média longa. Medidas de distribuição de massa de fragmentos emitidos e razão (ANTPOT. 16 O/ANTPOT. 12 C) sugerem que o mecanismo de reação no caso do sistema ANTPOT. 28 Si + ANTPOT. 16 O é de orbiting, não passando pela formação do núcleo composto. Cálculos de canais acoplados, incluindo grande número de canais populados nas reações, permitem reproduzir as distribuições angulares oscilantes e com forte subida em ângulos traseiros dos estados individuais, bem como as distribuições angulares integradas em Q, lisas, com comportamento 1/sen IND. CM para os sistemas ANTPOT. 18 O+ANTPOT. 10,11 B E ANTPOT. 28 Si + ANTPOT. 16 O. / The binary decay into strongly damped fragments and the quasielastic reactions of the systems 18O + 10,11B and 28Si + 16O were measured at ELAB(18O)=52.5 MeV, ELAB(28O)=107.5 e 139 MeV in the angular range of 30ºCM160º. In bolh systems the quasielastic angular distributions present oscillations and strong increase in the backward region. The angular distributions of the Q-value integrated cross-section follow the tendency 1/sinCM in both systems indicating a long life-time. Mass distribution measurement and the (16O/12C) ration suggest that the reaction mechanism in the case of the 28Si+16O system is orbiting/deep-inelastic. Coupled channels calculations, including a great number of the channels populated in the reactions yield angular distributions which agree well with experimental data for both systems.

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

Foram medidas distribuições angulares dos canais quase-elásticos e do decaimento em fragmentos binários fortemente amortecidos dos sistemas ANTPOT. 18 O+ANTPOT. 10,11 B E ANTPOT. 28 Si + ANTPOT. 16 O em energias de E IND. LAB(ANTPOT. 18 0) = 52,5 MeV e E IND. LAB(ANTPOT. 28 0) = 107,5 e 139 MeV. Em todos os sistemas, as distribuições angulares quase-elásticas apresentam oscilações com uma subida da seção de choque em ângulos traseiros. As distribuições integradas em valor de Q, apresentam o comportamento 1/sen IND. CM em todos os sistemas indicando uma vida-média longa. Medidas de distribuição de massa de fragmentos emitidos e razão (ANTPOT. 16 O/ANTPOT. 12 C) sugerem que o mecanismo de reação no caso do sistema ANTPOT. 28 Si + ANTPOT. 16 O é de orbiting, não passando pela formação do núcleo composto. Cálculos de canais acoplados, incluindo grande número de canais populados nas reações, permitem reproduzir as distribuições angulares oscilantes e com forte subida em ângulos traseiros dos estados individuais, bem como as distribuições angulares integradas em Q, lisas, com comportamento 1/sen IND. CM para os sistemas ANTPOT. 18 O+ANTPOT. 10,11 B E ANTPOT. 28 Si + ANTPOT. 16 O. / The binary decay into strongly damped fragments and the quasielastic reactions of the systems 18O + 10,11B and 28Si + 16O were measured at ELAB(18O)=52.5 MeV, ELAB(28O)=107.5 e 139 MeV in the angular range of 30ºCM160º. In bolh systems the quasielastic angular distributions present oscillations and strong increase in the backward region. The angular distributions of the Q-value integrated cross-section follow the tendency 1/sinCM in both systems indicating a long life-time. Mass distribution measurement and the (16O/12C) ration suggest that the reaction mechanism in the case of the 28Si+16O system is orbiting/deep-inelastic. Coupled channels calculations, including a great number of the channels populated in the reactions yield angular distributions which agree well with experimental data for both systems.

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

Popular catalytic cycles, such as the Heck, Suzuki, and Negishi, utilize metal centers that oscillate between two oxidation states (II/0) during the three main steps of catalysis: reductive elimination, oxidative addition, and transmetallation. There has been a push to use less toxic, cheaper metal centers in catalytic cycles, leading to interest in first-row transition metals, such as nickel and cobalt. With these metals, the cycles can potentially pass through the +1 oxidation state, which acts as reactive intermediates, undergoing oxidative additions to form products, potentially with radical characteristics. The oxidative addition steps of catalytic cycles are critical to determining overall rates and products, however in many cases, these steps have not been amenable to study, in either condensed phase or gas phase, in the past. Through the use of electron transfer dissociation (ETD) technology on a modified Thermo Electron LTQ XLTM mass spectrometer, it is possible to generate intermediates in these catalytic cycles, including those in unusual oxidation states. Using sequentially coupled ion/ion-ion/molecule reactions, the reduced, reactive intermediate can be readily generated, isolated, and studied.As a model set of reactions, the mono- and bis-phenanthroline complexes of Fe(I), Co(I), Ni(I), Cu(I), and Zn(I) were formed by reduction of the corresponding M(II) species in an ion/ion reaction with the fluoranthenyl radical anion. The chemistry of the M(I) species was probed in ion/molecule reactions with allyl iodide. In order to explore ligand effects and the scope of oxidative addition reagents further, bipyridine and terpyridine were studied with these five first-row transition metal complexes while using an acetate series and other substrates for oxidative additions. Through these studies, the roles of the metal and ligand in dictating the product distributions and reaction rates were assessed. Metal electron count, ligand flexibility, and coordination number are critical factors. The overall reactivity is in accord with density functional theory calculations and mirrors that of proposed intermediates in condensed-phase catalytic cycles. In addition, second- and third-row transition metals (Ru(I), Pd(I), and Pt(I)) were explored with bipyridine, mono- and bis-triphenylphosphine, and 1,2-bis(diphenylphosphino)benzene ligation schemes. A variety of oxidative addition reagents were surveyed to determine the scope of reactivity and preference toward metal-carbon bond formation or carbon radical formation.

No description available.

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