京都大学 / 新制・課程博士 / 博士(工学) / 甲第24625号 / 工博第5131号 / 新制||工||1981(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 松原 誠二郎, 教授 中尾 佳亮, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第25297号 / 工博第5256号 / 新制||工||2000(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 松原 誠二郎, 教授 中尾 佳亮, 教授 杉野目 道紀 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Les azaphosphatranes sont des entités relativement peu utilisées en catalyse organique. Cependant, ils se sont révélés être de bons catalyseurs pour la réaction de couplage entre des époxydes et le dioxyde de carbone pour former des carbonates cycliques. Les travaux de cette thèse portent sur l'optimisation de la réactivité des azaphosphatranes pour la synthèse de carbonates cycliques. Tout d'abord, une étude du confinement à différentes échelles a été réalisée. Les catalyseurs ont été étudiés en présence de silice mésoporeuse de type SBA-15 qui exacerbent leur activité. L'ajout d'un solvant ou de silice entraîne des modifications de mécanisme. La synthèse d'azaphosphatrane encagé au sein d'hémicryptophane a permis d'étudier l'effet d'un double confinement au sein d'une macromolécule et d'un matériau. Ensuite, les azaphosphatranes ont été fonctionnalisés à différentes positions par des groupements activateurs de l'époxyde ou du dioxyde de carbone. Enfin, différentes approches de synthèse de carbonates cycliques énantioenrichis ont été testées. La chiralité a été introduite par le biais de centres asymétriques sur les bras de l'azaphosphatrane ou par le confinement au sein d'un hémicryptophane chiral. Des silices chirales obtenues soit par empreinte moléculaire de proline ou par greffage covalent d’organosilanes chiraux ont également été testées. / Azaphosphatranes have rarely been applied as organocatalysts in organic transformations. Nevertheless, they have recently proved to be efficient single-component metal-free catalysts for the production of cyclic carbonates from epoxides and carbon dioxide. The goal of this work is to optimize the reactivity of azaphosphatrane based catalysts towards greater CO2 fixation into cyclic carbonates. First, they have been used in conjunction with mesoporous silica of the SBA family. A positive synergy, depending on the nature of the counter-anion, was demonstrated leading to better yields in cyclic carbonates. Adding a solvent or silica was shown to drive to a change in the reaction mechanism as evidenced by kinetic studies. Then, different activating functional groups were introduced at different position of the catalyst structure to further activate epoxide or carbon dioxide substrates. Finally, the kinetic resolution of racemic epoxides in the presence of CO2 was investigated. Different approaches to chiral induction have been explored including the introduction of asymmetric carbons on azaphosphatranes, the use of induced chirality with cyclotriveratrylene unit in hemicryptophane moiety. Chiral imprinted with amino acids and chiral grafted mesoporous silicas have also been studied.

Aldol addition reaction is one of the most important and most studied carbon-carbon bond forming reactions in organic chemistry. Recent studies focused on the catalytic version of this chemistry. Different from the classical Mukaiyama-type aldol reactions, chiral lewis bases have been used as promoters. In the presence of SiCl4, these reactions proceed through a cyclic transition state leading to anti aldol product as a major product with moderate-to-good diastereo and enantioselectivities. Phosphoramide derivatives, BINAPO, BINAPO derivatives, N,N-dioxides and N-oxides have been extensively used for this purpose. Recently, our group has designed new phosphine oxy aziridinyl phosphonates (POAP) as chiral Lewis bases. These promoters were used for the asymmetric aldol addition reaction between cyclohexanone and different aldehydes in the presence of SiCl4. Moreover, our previously designed phosphine oxy ferrocenyl substituted aziridinyl methanol (POFAM) ligands were also tested as Lewis bases. Among these 6 potential promoters, POAP-A gave the best results, and the aldol product were obtained in moderate to good yields up to 80%, and with moderate enantioselectivities (the highest, 66%) after standard optimization studies. Aldehyde screening experiments provided the highest enantioselectivity (68%) with 2- naphthaldehyde.

Chiral pyridines as organocatalysts have been used in asymmetric organic synthesis in recent years. The asymmetric synthesis of camphor fused pyridine type novel organocatalysts were perfomed starting from cheap and easily available natural (+)-camphor. Using camphor fused pyridine skeleton, six organocatalysts 29, 32, 33, 38, 40, and 41were successfully synthesized. The first four nucleophilic and Lewis base catalysts 29, 32, and 33 are different P-oxides and P,N-dioxides which were tested in allylation of aldehydes via allyltrichlorosilane. L-proline amide 38 and D-proline amide 40 can be named as secondary amine catalyst. They were tested in direct aldol reaction between acetone and aromatic aldehydes in aqueous medium. Final group of catalyst is hydrogen bonding type catalyst which is thiourea based 41.

Novel 1,4-chiral diamine ligand possessing a trans-9,10-dihydro-9,10-ethanoanthracene backbone was synthesized. The synthetic plan involves first LiAlH4 reduction of the Diels-Alder adduct obtained by reaction of dimenthyl fumarate and anthracene, which is followed by reacting the corresponding alcohol and subsequent attachment of mesylate and triflate units to get good leaving groups which are available substances for introducing nitrogen units via SN2 type reactions. Consequently, by using dimesyl ester and ditriflate esters five catalysts 27, 29, 30, 33 and 38 were synthesized. The first four catalysts 27, 29, 30 and 33 were used in transfer hydrogenation reactions with transition metal whereas catalyst 38 used as an organocatalyst in direct aldol reaction between acetone and p-nitrobenzaldehyde.

In the first part of this thesis, the construction of the novel bifunctional proline-(1R,2R)-2-aminoDMAP organocatalyst backbone is described. Target compound has both Lewis base and Br&oslash / nsted acid catalaphoric sites. The Lewis base site is synthesized via selective mono-N-pyridilization of trans-(1R,2R)-cyclohexane-1,2-diamine by Cu catalysis and Br&oslash / nsted acid site is subsequently introduced by anchoring L-proline unit. In the second part, catalytic activities of organocatalysts are tested in asymmetric Michael addition reaction between a cyclic 1,3-dicarbonyl compound 4-hydroxycoumarin and various &alpha / ,&beta / -unsaturated ketones to afford optically active warfarin as anticoagulants, in one step. Reaction parameters such as solvent, temperature, equivalency, and cocatalyst were screened. Enantiomeric excess value (ee) up to 72% is attained.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23036号 / 理博第4713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 時任 宣博, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Une synthèse racémique organocatalytique de pyrazolines 3,5-diaryl a été développée, grâce à l'utilisation d'une guanidine comme catalyseur. Ensuite, une synthèse énantiosélective de n-boc pyrazolines 3,5-diaryl a été mise au point sous catalyse par transfert de phase, atteignant des excès énantiomériques jusqu'à 94 %. Des réactions de transprotection du groupement Boc ont permis l'accès à une variété de substituants sur l'azote N1 de la pyrazoline. Ces développements ont été exploités dans la synthèse d'une pyrazoline biologiquement active. Nous avons exploité un biopolymère chiral, le chitosane, en aminocatalyse, comme organocatalyseur hétérogène. Après mise en forme des modifications chimiques du polymère, les matériaux obtenus ont été testés dans plusieurs réactions organocatalytiques. Un excès énantiomérique de 80 % a été atteint dans une réaction d'aldolisation. Enfin, la technologie de liquide ionique supporté sur chitosane a été appliquée à divers réactions organocatalysées. / An organocatalytic racemic synthesis of 3,5-diaryl pyrazolines was developed, using guanidine as catalyst. Then, an enantioselective synthesis of N-Boc 3,5 diarylpyrazolines under phase transfer catalysis, achieving high enantiomeric excesses up to 94 %. Transprotection reactions of the Boc moiety allowed the introduction of a variety of functional groups on N1 atom of the pyrazolines ring. Finally, we applied this strategy to the synthesis of biologically active pyrazoline. Secondly, we used the chiral biopolymer chitosan in aminocatalysis, as a heterogeneous organocatalyst. We performed chemical modifications either by grafting proline, or by a benzyl moiety leading to secondary polyamines. The obtained materials were tested in different organocatalytic reactions. A 80 % enantiomeric excess has been reached for an aldolisation reaction. Finally, we applied, for the first time, the ionic liquid supported phase strategy on chitossan for aour organocatalysed reactions.