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

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.