Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第13828号 / 工博第2932号 / 新制||工||1433(附属図書館) / 26044 / UT51-2008-C744 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 檜山 爲次郎, 教授 大嶌 幸一郎, 教授 松原 誠二郎 / 学位規則第4条第1項該当

The diverse biological properties exhibited by uridine analogues modified at carbon-5 of the uracil base have attracted special interest to the development of efficient methodologies for their synthesis. This study aimed to evaluate the possible application of vinyl tris(trimethylsilyl)germanes in the synthesis of conjugated 5-modified uridine analogues via Pd-catalyzed cross-coupling reactions. The stereoselective synthesis of 5-[(2-tris(trimethylsilyl)germyl)ethenyl]uridine derivatives was achieved by the radical-mediated hydrogermylation of the protected 5-alkynyluridine precursors with tris(trimethylsilyl)germane [(TMS)3GeH]. The hydrogermylation with Ph3GeH afforded in addition to the expected 5-vinylgermane, novel 5-(2-triphenylgermyl)acetyl derivatives. Also, the treatment with Me3GeH provided access to 5-vinylgermane uridine analogues with potential biological applications. Since the Pd-catalyzed cross-coupling of organogermanes has received much less attention than the couplings involving organostannanes and organosilanes, we were prompted to develop novel organogermane precursors suitable for transfer of aryl and/or alkenyl groups. The allyl(phenyl)germanes were found to transfer allyl groups to aryl iodides in the presence of sodium hydroxide or tetrabutylammonium fluoride (TBAF) via a Heck arylation mechanism. On the other hand, the treatment of allyl(phenyl)germanes with tetracyanoethylene (TCNE) effectively cleaved the Ge-C(allyl) bonds and promoted the transfer of the phenyl groups upon fluoride activation in toluene. It was discovered that the trichlorophenyl,- dichlorodiphenyl,- and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of TBAF in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two or three phenyl groups from the organogermane precursors. The methodology shows that organogermanes can render a coupling efficiency comparable to the more established stannane and silane counterparts. Our coupling methodology (TBAF/moist toluene) was also found to promote the transfer of multiple phenyl groups from analogous chloro(phenyl)silanes and stannanes.

Thesis advisor: Jeffery A. Byers / This dissertation discusses the development of iron-based catalysts for Suzuki-Miyaura cross-coupling reactions and some of the unique reactivity that was discovered as a direct result of these studies. Chapter one will review the area of iron-catalyzed cross-coupling with an emphasis placed on areas where iron provides complimentary reactivity to other metals. Chapter two will detail the initial discovery of conditions that allow for iron-catalysts to participate in the cross-coupling of aryl boronic esters and alkyl halides. Chapter three will discuss the the development of ligands for iron that allow for more general cross-coupling reactivity to be observed. Finally, chapter four will discuss the unique C-H funtionalization reactivty that has been observed as byproducts in chapters two and three. Digging deeper into this reactivty lead to the discovery of a completely novel three-component coupling reaction mediated by the iron complexes discovered in chapter three. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Oxygen and Nitrogen containing compounds are of utmost importance due to their interesting and diverse biological activities. The construction of the C-O and C–N bonds is of significance as it opens avenues for the introduction of ether and amine linkages in organic molecules. Despite significant advancements in this field, the construction of C-O and C–N bonds is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts or ligands in many cases. Thus, it is a challenge to develop alternative, milder, cheaper and more reproducible methodologies for the construction of these types of bonds. Herein, we introduce a new efficient ligand free catalytic system for C-O and C-N bond formation reactions.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19516号 / 理博第4176号 / 新制||理||1600(附属図書館) / 32552 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 丸岡 啓二, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20205号 / 理博第4290号 / 新制||理||1616(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 依光 英樹, 教授 大須賀 篤弘, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21784号 / 工博第4601号 / 新制||工||1717(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 中村 正治, 教授 近藤 輝幸, 教授 村田 靖次郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13456号 / 論工博第4196号 / 新制||工||1770(附属図書館) / (主査)教授 中村 正治, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Progress toward the syntheses of new tetranuclear bimetallic complexes of copper(II) and ruthenium(II) was realized. The designed triads comprise a central binuclear copper(II) complex with a tetraiminodiphenolate macrocyclic Robson-type compartmental ligand. In the envisioned complexes, the macrocyclic core is further functionalized by attachment of two polypyridyl ruthenium(II) complexes. A novel dibrominated dicopper(II) Robson complex was formed by the 2:2:2 condensation reaction of 4-bromo-2,6-diformylphenol and 1,3- diaminopropane with cupric chloride. Similarly, a new dibrominated dizinc(II) was synthesized from zinc tetrafluoroborate and the same diamine and dialdehyde. The new dicopper(II) complex did not heterocouple with borylated substrates under explored Suzuki reaction conditions. 5-Bromo-2-(methoxymethoxy)benzene-1,3-dicarboxaldehyde successfully heterocoupled with 4-tert-butylphenylboronic acid under Suzuki conditions. 4'-(4-Neopentylglycolatoboronphenyl)-2,2':6',2-terpyridine also coupled with 5-bromo-2-(methoxymethoxy)benzene-1,3-dicarboxaldehyde to give, after deprotection, 2,6-diformyl-4-(4-[2,2':6',2"-terpyridin]-4'-ylphenyl)phenol. This new dialdehyde, a precursor to the title complexes, was treated with (4'-(4-methylphenyl)-2,2':6',2"-terpyridine)RuCl3 under reducing conditions; however, the desired [(4'-(4-methylphenyl)-2,2':6',2"-terpyridine)Ru(4'-(3,5-diformyl-4-hydroxyphenyl)-2,2':6',2"-terpyridine)]2+ was neither isolated from nor detected in the reaction mixture.

The catalysis reaction performance, such as yield, is very crucial in organic chemistry. And predicting the reaction yield is still very challenging. In this thesis, machine learning is used to predict the reaction yield in a C–N cross-coupling approach. The reaction data are from the high-throughput experimental data with four variables: reactants, Pd catalysts, additives, and bases. Each reaction data will give the corresponding yield. The data are from the literature, which has been uploaded. The total data number used in machine learning is 7910. The method mainly consists of four steps. First, load the csv data and import modules. Second, encode data with molecular fingerprint or one-hot encoding. The data will be normalized if there is need. Third, split the dataset into train and test set with the size ratio of 7/3 or 8/2. Fourth, use six machine learning models to learn the data and evaluate their performance. Then, compare the prediction yield of the test set. The accuracy in prediction (RMSE value and R-squared) and running time will be considered for evaluation. By comparing the RMSE and R-squared values of different models, we can decide which one has better performance and better fitting results. Improved reaction performance, or high-performance catalysts and their characteristics may be obtained.