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The recently discovered cucurbit[n]uril are a range of macrocyclic hosts which have enormous potential in industrial, medical and academic applications. Cucurbit[n]uril have a rigid repeating structure of methylene bridged glycouril, which give cucurbit[n]uril their gourd like shape of a cavity with two carbonyl fringed portals. In this thesis the host-guest binding abilities of three cucurbit[n]uril (n = 6, 7, 8) have been examined for a range of potential guests. These guests ranged from simple alkyl amines through globular alkyl and carboranyl amines to bipyridyl systems. In total 45 guest molecules where examined. Most of the guests examined where either cationically charged, capable of hydrogen binding, contained a substantial molecular dipole, or a combination of these. Furthermore, all of the potential guests examined had some solubility in an acidified aqueous sodium sulfate solution within which the host-guest properties were examined. It was generally found that the larger guests did have selectivity for the larger hosts. However, when the host became too large weaker complexes would form and for the range of materials examined here cucurbit[7]uril was found to be the 'best' host system. In one example, p-xylene diamine, a 2:1 complex with cucurbit[8]uril was observed. While not the focus of this work a new rapid purification method was developed for the cucurbit[n]uril using different metal ions to either solubilise or precipitate the different cucurbit[n]uril. In the second part of this work these same guest molecules where used as potential templates in the synthesis of cucurbit[n]uril. Surprisingly the guests that bound strongly to an individual host did not seem to template the cucurbit[n]uril synthesis at all. Rather these strong binders inhibited the reaction such that little or no cucurbit[n]uril formed under the reaction conditions studied. However, several examples provided excellent template results. Indeed the results indicate that guests which bound with intermediate rates of exchange are the best templates and using templates under these conditions we have been able to produce cucurbit[7]uril as 46% by mass of the total cucurbit[n]uril product. This is the highest yield ever recorded for cucurbit[7]uril and it is the first example of cucurbit[7]uril being the major product of this condensation reaction. In an another example cucurbit[8]uril formed 18% of the product an increase of 150% over the standard reaction conditions. While studying both the template reactions and the host-guest binding properties of the cucurbit[n]uril a new supramolecular form, an 'inverse rotaxane' was discovered. Inverse rotaxanes are not held in place by large blocking groups, rather the molecular structure encapsulated by the cucurbit[n]uril host prevents decomplexation of the axle.

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane- materials can be engineered for drug delivery and adsorption. The phase behavior of polymerizing mixtures is first investigated to identify the solutions that favor kinetic characterization. Microphase separation is found to cause gradual loss of NMR signal for certain initial compositions. Distortionless Enhancement by Polarization Transfer 29Si NMR is employed to identify the products of polymerization of some short-bridged silanes under no signal loss conditions. This technique requires knowing indirect 29Si-1H scalar coupling constants which sometimes cannot be measured due to second-order effects. However, the B3LYP density functional method with 6-31G basis set is found to predict accurate 29Si-1H coupling constants of organoalkoxysilanes and siloxanes. The scalar coupling constants thus estimated are employed to resolve non-trivial coupled NMR spectra and quantitative kinetic modeling is performed using the DEPT Si NMR transients. In order to investigate the role of the organic bridging group, the structural evolution of bridged and non-bridged silanes are compared using Monte Carlo simulations. Kinetic and simulation models suggest that cyclization plays a key role right from the onset of polymerization for bridged silanes even more than in non-bridged silanes. The simulations indicate that the carbosiloxane rings formed from short-bridged precursors slow down but do not prevent gelation. The tuning of siloxane-based materials for adsorption technologies are also discussed here. In the first example, antioxidant enzyme loading is investigated as a means to reduce oxidative stress generated by silica nanoparticle drug carriers. Materials are engineered for promising enzyme loading and protection from proteolysis. Second, the potential of copper sulfate impregnation to enhance adsorption of ammonia by silica is explored by molecular simulation.

Gold catalysis has become an important tool to achieve highly chemoselective p-acid activation. Exceptional reactivity and selectivity are often encountered under mild reaction conditions. These properties have made gold(I) complexes suitable catalysts for tremendous applications in the total synthesis of natural products. The first chapter will highlight a number of total syntheses using gold catalysis as a key step. The second chapter will cover our application of the gold(I)-catalyzed 6-endo-dig carbocyclization for the synthesis of bridgehead-substituted scaffolds and its use toward the synthesis of PPAP natural products. This research has opened our eyes to the utility of biphenylphosphine ligands, particularly JohnPhos, in gold(I)-catalysis. The reactivity and selectivity exhibited by gold(I) complexes is modulated by the nature of the ancillary ligand. Recent research rationalizes the impact of these ligands on the divergent reactivity observed between cationic and carbenoid intermediates. Our desire to favor the 6-endo-dig pathway has led us toward the discovery of another example of the diagonal reactivity that NHC carbene and biphenylphosphine ligands can bring to gold(I)-catalysis. Chapter three will explain the development of a selective gold-catalyzed synthesis of fused carbocycles . Our selective divergent synthesis of fused carbocycles, combined with the Diels–Alder reaction, has brought new synthetic opportunities. Chapter four will describe our approach toward the synthesis of various polycyclic diterpene-related frameworks. Starting with a unique linear precursor, we have developed a new “one-pot” process for the synthesis of three different polycyclic compounds related to the terpenoid family. The facile modulation of the linear precursor and the use of different dienophiles during the Diels–Alder reaction could enable the synthesis of diverse polycyclic analogues based on three principal frameworks. The gold(I)-catalyzed synthesis of fused carbocycles reached some limitations during our study. Regioselective control was found to be substantially more challenging, with terminal alkynes or alkynes bearing a sterically and electronically neutral methyl substituent. In chapter five, we will discuss how the complementarity of silver(I) catalysis to gold(I) catalysis enabled the selective divergent synthesis of three different fused carbocycles from a unique precursor. Moreover, copper(I) catalysis has given access to the 6-endo-dig pathway on terminal alkynes without the formation of a vinylidene intermediate.

ABSTRACT ELECTROCHEMICAL SYNTHESIS OF CROWNED CONDUCTING POLYMERS: NATURE OF RADICAL CATIONS IN POLYMERIZATION AND MECHANISM OF CONDUCTIVITY Cihaner, Atilla Ph. D., Department of Chemistry Supervisor: Prof. Dr. Ahmet M. &Ouml / nal June 2004, 96 Pages Poly(dibenzo-18-crown-6) (Poly(DB18C6)) was synthesized by electrochemical oxidation of dibenzo-18-crown-6 (DB18C6) using a mixture of acetonitrile and dichloromethane as solvent and tetrabutylammonium tetrafluoroborate (TBABF4) or tetrabutylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. The anodic polymerization of DB18C6 was investigated using in-situ ESR and in-situ UV-VIS spectroscopic techniques. Spectroelectrochemical (SPEL) properties and thermal analysis of the resulting polymers have been investigated using UV-VIS, Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA). Furthermore, new compounds consisting of bis(2-thienyl) methyl (I and II) and bis(2-thienyl) ethyl (III) units linked by polyether bridges have been synthesized and their electrochemical polymerization was performed via constant potential electrolysis (CPE) in an electrolytic solution containing 0.1 M TBAPF6 dissolved in CH3CN. Also, I and II were polymerized via chemical oxidation which yielded broken &amp / #61552 / -conjugated polymers except for III. The polymers were characterized using 1H-NMR and FT-IR spectroscopic techniques. In addition, copolymers of III with thiophene (Th) and pyrrole (Py) were studied with cyclic voltammetry (CV). SPEL behaviors of the products were investigated using UV-VIS spectroscopic technique.

Effective adsorbents for polyfluorinated compounds (PFCs) were successfully prepared. And they were tested in the adsorption of perfluorooctanoic and perfluorooctanesulfonic acids. Bridged silsesquioxanes containing secondary and tertiary amino groups were synthesized by sol-gel condensation of bis[3-(trimethoxysilyl)propyl]amine and bis[3-(methylamino)propyl]-trimethoxysilane in acidic media with surfactants. Obtained materials are mesoporous with a high BET surface area. They combine high structural stability with a high concentration of surface amino groups serving as adsorption sites. Batch adsorption tests demonstrated their extremely high adsorption capacity on PFCs: in some experiments, it reached up to 88% of the adsorbent weight. Adsorption of PFCs changed the surfaces of the adsorbent nanoparticles from hydrophilic to hydrophobic thus providing their agglomeration and floatability. Column tests showed fast adsorption of PFCs even at high concentrations and high flow rates. Obtained results can be used in the development of an effective filtration device for clean-up of water contaminated by PFCs.

Gold catalysis has become an important tool to achieve highly chemoselective p-acid activation. Exceptional reactivity and selectivity are often encountered under mild reaction conditions. These properties have made gold(I) complexes suitable catalysts for tremendous applications in the total synthesis of natural products. The first chapter will highlight a number of total syntheses using gold catalysis as a key step. The second chapter will cover our application of the gold(I)-catalyzed 6-endo-dig carbocyclization for the synthesis of bridgehead-substituted scaffolds and its use toward the synthesis of PPAP natural products. This research has opened our eyes to the utility of biphenylphosphine ligands, particularly JohnPhos, in gold(I)-catalysis. The reactivity and selectivity exhibited by gold(I) complexes is modulated by the nature of the ancillary ligand. Recent research rationalizes the impact of these ligands on the divergent reactivity observed between cationic and carbenoid intermediates. Our desire to favor the 6-endo-dig pathway has led us toward the discovery of another example of the diagonal reactivity that NHC carbene and biphenylphosphine ligands can bring to gold(I)-catalysis. Chapter three will explain the development of a selective gold-catalyzed synthesis of fused carbocycles . Our selective divergent synthesis of fused carbocycles, combined with the Diels–Alder reaction, has brought new synthetic opportunities. Chapter four will describe our approach toward the synthesis of various polycyclic diterpene-related frameworks. Starting with a unique linear precursor, we have developed a new “one-pot” process for the synthesis of three different polycyclic compounds related to the terpenoid family. The facile modulation of the linear precursor and the use of different dienophiles during the Diels–Alder reaction could enable the synthesis of diverse polycyclic analogues based on three principal frameworks. The gold(I)-catalyzed synthesis of fused carbocycles reached some limitations during our study. Regioselective control was found to be substantially more challenging, with terminal alkynes or alkynes bearing a sterically and electronically neutral methyl substituent. In chapter five, we will discuss how the complementarity of silver(I) catalysis to gold(I) catalysis enabled the selective divergent synthesis of three different fused carbocycles from a unique precursor. Moreover, copper(I) catalysis has given access to the 6-endo-dig pathway on terminal alkynes without the formation of a vinylidene intermediate.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24872号 / 理博第4982号 / 新制||理||1711(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 有賀 哲也, 教授 堀毛 悟史 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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