Fast development in all areas of life and science over the last 50 years demands versatile, energy efficient and cheap materials with specific but easily tuneable properties which can be used for example in organic light emitting diodes (OLEDs), thin-film transistors, photovoltaic cells, etc. This thesis is devoted to the development of novel synthetic approaches to molecules with potential applications in the field of molecular electronics.  The acquisition of a detailed mechanistic understanding of the newly developed reactions is central to the work presented in this thesis. The first chapter is dedicated to the development of a new procedure for the preparation of phospha-Wittig-Horner (pWH) reagents, i.e. a reagents that has been known to convert carbonyl compounds into compounds with P=C double bonds. Each step of the synthetic sequence, i.e. preparation of the starting P,P-dichlorophosphines, their phosphorylation using the Michaelis-Arbuzov protocol, coordination to the metal centre and final hydrolysis, are presented in detail. A possible route to uncoordinated pWH reagents is also discussed. The second chapter focuses on the reactivity of the pWH reagents with acetone under different reaction conditions. The results show how changes in the ratio of starting material vs. base as well as reaction time or structure of the pWH reagent can influence the reaction outcome and the stability of the obtained products. The possibility to prepare unusual phosphaalkenes with unsaturated P-substituents is presented. The third chapter of the thesis is dedicated to the reactivity of pWH reagents towards symmetric and asymmetric ketones which contain one or two acetylene units. The proposed mechanisms of the reactions are studied by means of in situ FTIR spectroscopy as well as theoretical calculations. Physical-chemical properties of oxaphospholes, cumulenes and bisphospholes are presented. The last chapter is dedicated to reactivity studies of pWH reagents towards ketenes, and the exploration of a reliable route to 1-phosphaallenes. Detailed mechanistic studies of the pWH reaction that are based on the isolation and crystallographic characterization of unique reaction intermediates are presented. The reactivity of phosphaallenes towards nucleophiles such as water and methanol are examined. In summary, this thesis presents synthetic routes to novel phosphorus-containing molecules, together with detailed studies of the reaction mechanisms of the observed transformations.

Steroid sulfatase (STS) catalyzes the desulfation of sulfated steroids such as estrone sulfate to the corresponding steroid such as estrone. Inhibitors of STS are believed to have potential for treating estrogen-dependent breast cancer. A new class of potential irreversible suicide inhibitors of STS, based on aryl sulfates bearing a monofluoromethyl or difluoromethyl group ortho to the sulfate group, was synthesized. Key to the success of these syntheses was the use of new sulfation methodology recently developed in the Taylor group. A new and efficient route to 4-formyl estrone, a time-dependent, irreversible STS inhibitor, is also reported. Several new classes of potential, reversible STS inhibitors were synthesized. These compounds are analogs of known STS substrates in which the sulfate group is replaced with an ,-difluoromethylenesulfonamide group, a boronic acid group or a sulfinic acid group. We also report the synthesis of estrone sulfate analogs that bear a carboxylate moiety at the 17-position and a sulfate surrogate at the 3-position. It is anticipated that these compounds will inhibit STS by interacting with Arg98 which lies at the periphery of the active site. Key to the success of this synthesis was the use of the t-butyl group as a protecting group for the 2-position of estrone. Finally, our preliminary investigations into the synthesis of a new class of chiral electrophilic fluorinating agents are presented. These reagents are based on a chiral binaphthyl sulfonimide scaffold and are expected to be capable of performing enantioselective electrophilic fluorinations. Such reagents may be useful in synthesizing organofluorines of biological significance including STS inhibitors.

Conducting polymers have been widely explored for many different purposes including sensing. In thisthesis the conducive properties of pyrrole and the carbohydrate binding properties of boronic acid iscombined to make a reagent-free detector for carbohydrates. The polymer is manufactured in form ofparticles in the μm scale to create a porous film which has a high surface to volume ratio.The material was characterised and the binding properties were evaluated for galactose and glucose.Proof of binding was found via both electrochemical methods and QCM-D. A correlation between R2 value and concentration of substrate was found which enables measurement of concentration of carbohydratesin unknown samples.

The synthesis, structure, and reactivity of some organometallic-fusedheterocycles were studied. This work was divided into three parts: first,thiapentalenyl tricarbonyl manganese complexes [Mn(CO)3{??5-SC7H3-1,3-(R)2}]were synthesized employing thiation on diacyl precursors; second, attempts toform the 5,5-fused ring pyrrole analogs to the thiapentalenyl complexes led to theformation of various amine and imine ligands and manganese complexes, but notthe desired ring-closed pyrroles; third, reductive amination on a ferrocenylmonoaldehyde substrate led to the formation of di(N-(ferrocenylmethyl))-Nmethylamineand its cyanoborane and cyanoborohydride analogs.Isolation of the desired thiapentalenyl manganese complexes wasaccomplished by first forming 1,2-diacylcyclopentadienes (fulvenes), convertingto the corresponding thallium salts [Tl{1,2-C5H3(COR)2}] employing thalliumethoxide, transmetallating with [Mn(CO)5Br], and ring closing using either P4S10or Lawesson's Reagent. Ring closure from the diacylmanganese complexes[Mn(CO)3{??5-1,2-C5H3(COR)2}] gave air stable thiapentalenyl complexes inmoderate to good yield and was tolerable to a variety of functional groups (aryl,arylacetyl, t-butyl). In the cases where 1,2-diarylacetyl complexes wereemployed, the isolated products were "quinoidal". While ring closure on thecorresponding diacylrhenium tricarbonyl complexes was not feasible, it wasobserved that these quinoidal thiapentalenyl structures could be formed on aruthenium Cp* moiety using the arylacetyl fulvenes.Various keto-amines or enol-imines could be formed from the 1,2-dibenzoyl fulvene employing primary amines (R = H, Me, OH, OMe). In thepresence of a reducing agent, neither reduction nor ring closure was observedfor any of the cases investigated. Formation of the corresponding manganesetricarbonyl complex for the methyoxyimine case was accomplished by reaction ofthe enol-methoxyimine with thallium ethoxide and then transmetallating with[Mn(CO)5Br]. Reaction of this keto-imine complex with various reducing agentsdid not lead to the desired 5,5-fused ring pyrrole complex but to reduction to thecorresponding alcohol.Diferrocenylmethyl methylamine complexes were obtained by reaction offerrocene monoaldehyde with ferrocenylmethyl methylamine in the presence of amild reducing agent (NaCNBH3). Isolation under anhydrous conditions gave theunexpected cyanoborohydride salt, di(N-(ferrocenylmethyl))-N-methylammoniumcyanoborohydride. Aqueous work-up gave the corresponding free amine.Conversion of the cyanoborohydride salt to the corresponding cyanoborane,di(N-(ferrocenylmethyl))-N-methylammonium–cyanoborane, was accomplishedby refluxing the cyanoborohydride salt in THF.

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 207-225).

Diss. (sammanfattning) Stockholm : Karolinska institutet, 2006. / Härtill 5 uppsatser.

Thesis (Ph. D.)--University of Alabama at Birmingham, 2008. / Title from first page of PDF file (viewed Sept. 16, 2008). Includes bibliographical references (p. 208-224).

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19518号 / 理博第4178号 / 新制||理||1600(附属図書館) / 32554 / 京都大学大学院理学研究科化学専攻 / (主査)教授 丸岡 啓二, 教授 時任 宣博, 教授 大須賀 篤弘 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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