With the increasing realization of their involvement in numerous biological processes, synthetic oligosaccharides present promising potential in drug and vaccine discovery. Selective functionalization of hydroxy groups in polyols represent a long-standing goal in chemistry since the chemical synthesis of O-glycosides often requires extensive protecting group manipulation. Organoboron catalysis is a recent strategy for regioselective activation of the equatorial hydroxy group of cis-vicinal diols. Following the initial findings that diarylborinic acid catalyzes the regioselective acylation of carbohydrate derivatives, kinetic studies were conducted to obtain better insight on the mechanism. Thereafter, the ability of diarylborinic acid to catalyze the regioselective alkylation of carbohydrates was demonstrated. Finally, investigations in the capability of diarylborinic acid to influence regiochemical outcome of glycosylation reactions were explored. Similarly, kinetic experiments were devised to shed light on the mechanism of the reaction.

In this work the alkylation of 2-ethylsulfanyl -5-methoxy-4(3H)-pyrimidinone with 4-substituted ω-bromoacetophenones, ethyl 2-bromoalkanoates and 1-bromomethyl-o-carborane was investigated. It was found that reaction of title compounds in the presence of potassium carbonate in boiling acetonitrile yielded O-alkylated derivatives with small amount of N3- and N1-alkylation products. The proportion of O- and N-alkylated products varied depending on the nature of substituent in the 4th position of benzene ring. Alkylation of title compound with ethyl bromoethanoate led to mixture of O-, N3- and N1 alkylated derivatives, while the reaction with ethyl 2-bromopropanoate yielded only O-alkylated isomer. 2-Substituted 4-pyrimidinols with nido-carborane at the side chain were synthesized. The structure of synthesized compounds was confirmed by the data of IR, UV and 1H NMR spectra.

<p><b><font face="TimesNewRomanPS-BoldMT"> <p align="left">Apoptosis is a process in which a cell programmes its own death. It is a highly organized physiological mechanism in which injured or damaged cells are destroyed. Apart from physiological stimuli however, exogenous factors can induce apoptosis. Many anti-cancer drugs work by activating apoptosis in cancer cells. Natural substances have been found to have the ability to induce apoptosis in various tumour cells and these substances have been used as templates for the construction of novel lead compounds in anticancer treatment. On the other hand, alkylating agents such as cisplatin, cis- [PtCl2 (NH3) 2]have been widely used as antineoplastic agents for a wide variety of cancers including testicular, ovarian, neck and head cancers, amongst others. However, the use of cisplatin as an anticancer agent is limited due to toxicity and resistance problems. <font face="TimesNewRomanPSMT">The aim of this present study was to screen the leaves of </font><i><font face="TimesNewRomanPS-ItalicMT">Rhus laevigata</font><font face="TimesNewRomanPSMT">, a South African indigenous plant, for the presence of pro-apoptotic and anti-proliferative natural compounds and also to screen newly synthesised palladium based complexes (15 and 57) and a platinum based complex (58) for their antineoplastic activities tested against a panel of cell lines.</font></i></p> </font><font face="TimesNewRomanPS-BoldMT"> <p align="left">&nbsp / </p> </font></b></p>

Inaug.-Diss.--Basel. / Curriculum vitae.

Inaug.-Diss.--Basel. / Curriculum vitae.

Thesis (doctoral)--Ludwig-Maximilians-Universität München, 1960. / Vita. Includes bibliographical references (p. 79-80).

No contexto de refino de petróleo, alquilação é o processo pelo qual se produz uma corrente de hidrocarbonetos chamada de alquilado, na faixa da gasolina, a partir de olefinas leves (propeno, butenos) e isobutano. A demanda por alquilado como corrente integrante do pool de gasolinas de uma refinaria tem aumentado ao longo das duas últimas décadas devido a diversos fatores, sendo o principal a adoção de normas mais restritivas para a qualidade de combustíveis automotivos. No presente trabalho foi desenvolvido e validado um modelo matemático fenomenológico capaz de representar adequadamente as reações químicas envolvidas no processo de alquilação catalítica que utiliza ácido fluorídrico como catalisador, bem como estimar o rendimento de produto e subprodutos da reação e a qualidade do alquilado, representada pelo teor de tri-metil-pentanos (TMP) e di-metil-hexanos (DMH) no alquilado. A construção do modelo foi baseada em balanços de massa e energia no conjunto reacional, utilizando mecanismos cinéticos disponíveis na literatura, sendo os seus parâmetros cinéticos estimados por regressão não linear a partir de literatura. O modelo foi validado com dados obtidos em uma unidade industrial de propriedade da Petrobrás, localizada em Cubatão. Os resultados obtidos permitem afirmar que o modelo apresentou boa resposta para a identificação do consumo de reagentes e rendimento de produtos. Sua resposta tendeu a subestimar a quantidade de frações pesadas do alquilado. / Alkylation is the process which light hydrocarbons (like butenes and iso-bute) are transformed into heavier hydrocarbons, called alkylate. The alkylate demand as a gasoline component has been growing since the middle 90s, mostly due to more severe quality requirements for gasoline. This work proposes a mathematical model that accounts for the main chemical reactions for a HF Alkylation Unit. The alkylate yield and quality, described by its composition, are also represented as well. This model as based on mass and energy balances for the alkylation reactor, using the most accepted kinetic mechanism available at literature. The model constants were estimated by non-linear regression with available data from literature. The model validation was performed comparing the simulation results with data collected at an industrial Alkylation unit at Cubatão, Brazil, without further parameter adjustment. The results show a good model response for the consumption of reagents and alky yield. The model, however, underpredicts the yield of heavier fractions.

Thesis advisor: X. Peter Zhang / Asymmetric C–H functionalization represents one of the central topics in modern organic chemistry, which allows for the direct installation of functional groups onto ubiquitous C–H bonds in organic molecules. Among numerous elegant strategies, transition metal-catalyzed C–H alkylation with diazo compounds represents one of the most powerful methods for C–C bond formation. Different from Fischer metallocarbene-based C–H insertion reactions, cobalt(II)-based metalloradical catalysis (MRC) is recently proven to be capable of activating acceptor/acceptor diazo compounds for radical C–H alkylation reactions via H-atom abstraction. In this dissertation, we have developed several systems by utilizing less-explored aryl and alkyl diazomethanes as new radical precursors for highly enantioselective radical C–H alkylation reactions, which permit the efficient synthesis of different optically active heterocyclic compounds. First, we have demonstrated the feasibility of using aryl aldehyde-derived sulfonylhydrazones as new radical precursors for enantioselective radical C–H alkylation to synthesis enantioenriched 2,3-dihydrobenzofuran derivatives. Notably, a general and mild way for in situ generation of diazo compounds have been identified by using 2,4,6-triisopropyl sulfonyl hydrazone as diazo precursor, which allow us to regulate the reaction temperature to achieve the high enantioselectivity for the desired radical reactions. Second, the utility of Co(II)-based MRC has been further highlighted by enantioselective indoline synthesis. Through the design and synthesis of new catalysts, the system is shown to have a broad spectrum of substrate scope, forming various 2-substituted indolines with up to 98% yield and 96% ee. A series of mechanistic studies further support the underlying stepwise radical alkylation pathway. Finally, we further expand the applicability of MRC to even more challenging diazo compounds, aliphatic diazomethanes. Starting from alkyl aldehyde-derived sulfonylhydrazones as diazo precursors, the Co(II)-based radical alkylation reactions allow for the enantioselective synthesis for common 2-substituted tetrahydrofuran structures with high yields and excellent enantioselectivities. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23029号 / 理博第4706号 / 新制||理||1675(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 加納 太一, 教授 依光 英樹, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23214号 / 工博第4858号 / 新制||工||1758(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 中尾 佳亮, 教授 松原 誠二郎, 教授 大江 浩一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM