Development of Porous Ceramic-Immobilized Lipase Catalyst and Optically Active Fluorinated supramolecules

多孔陶瓷固定化脂肪酶催化剂及光学活性含氟超分子的研制

• 批准号: 13555255
• 负责人: SAKAI Takashi
• 金额: $ 8.7万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555255/
• 关键词: ceramic; kinetic resolution; immobilized lipase; enzyme; fluorine; asymmetric catalysis; asymmetric synthesis; basicity; リパーゼ; 固定化触媒; 架橋剤; 分子間相互作用; 不斉配位子

(1) Development of highly effective and enantioselective catalysis system with immobilized lipase at very low temperatures.(a) For development of an immobilized lipase, we searched the organic bridges coated on porous ceramic support. The organic bridges were combined with porous ceramic by, covalent bonding. When the organic bridge containing isobutyric acid ester moiety was used for the lipase-catalyzed resolution of racemic alcohols, both of enantioselectivity and catalytic activity of the immobilized lipase were much enhanced at -30℃.(b) For further improvement of efficiency of the immobilized lipase, we optimized the acylating agents. When vinyl butanoate was used as the acylating agent, both of the enantioselectivity and the catalytic activity were maximized at -40℃.(2) Development of the optically active fluorinated amines and their application to supramolecular materials.(a) An enantiomerically pure cyanohydrine containing pentafluorophenyl group was obtained by using lipase-catalyzed, resolution. The novel enantiomerically pure 1,2-aminoalcohol containing pentafluorophenyl and phenyl group was synthesized from the chiral cyanohydrine. The X-ray analysis of the compound indicated existence of the interaction between pentafluorophenyl group and alcoholic oxygen atom. The interaction afforded new and useful informations for designing supramolecular materials.(b) The novel enantiomerically pure 1,2-diamine containing pentafluorophenyl groups was synthesized via imino-pinacol coupling reaction. The basicity of the diamine was reduced as compared with the non-fluorinated derivative due to the strong electron-withdrawing ability of the pentafluorophenyl groups. The facts showed the influence of the pentafluorophenyl groups for the nitrogen atom.

（1）在非常低的温度下，用固定的脂肪酶开发了固定的脂肪酶。使用抗酸性脂肪酶在-30°C中使用抗酸性脂肪酶的Tase酸eSTY hothoChols h，并在-30°C上大大增强了脂肪酶在-40°C下最大化活性的氟化胺和超分子材料的发育。化合物表明存在五氟苯基基团和酒精氧原子，用于设计通过伊米诺菌偶联反应的基础知识的超分子材料。 ophenyl群。

项目成果

Sakai, T., Korenaga, T., Washio, N., Nishio, Y., Minami, S., Ema, T.: "Synthesis of Enantiomerically Pure (R, R)- and (S, S)-1,2-Bis(penta-fluorophenyl)ethane-1,2-diamine and Evaluation of the pK_a Value by ab initio Calculations."Bull.Chem.Soc.Jpn.. 80(i

Sakai, T.、Korenaga, T.、Washio, N.、Nishio, Y.、Minami, S.、Ema, T.：“对映体纯 (R, R)- 和 (S, S)-1 的合成，

Sakai, T., Matsuda, A., Korenaga, T., Ema, T.: "Practical Resolution of 3-Phenyl-2H-azirine-2-methanol at Very Low Temperature by Using Lipase Immobilized on Porous Ceramic and Optimized Acylating Agent."Bull.Chem.Soc.Jpn.. 76(9). 1819-1821 (2003)

Sakai, T.、Matsuda, A.、Korenaga, T.、Ema, T.：“使用固定在多孔陶瓷上的脂肪酶和优化的酰化剂在极低温度下实际拆分 3-苯基-2H-氮丙啶-2-甲醇

Takashi Sakai: "Practical Resolution of 3-Phenyl-2H-azirine-2-methanol at Very Low Temperature by Using Lipase Immobilized on Porous Ceramic and Optimized Acylating Agent."Bulletin of the Chemical Society of Japan. 76・9. 1819-1821 (2003)

Takashi Sakai：“使用固定在多孔陶瓷上的脂肪酶和优化的酰化剂在极低温度下实际拆分 3-苯基-2H-氮丙啶-2-甲醇”。日本化学学会公报 76・9。 (2003)

Sakai, T., Matsuda, A., Korenaga, T., Ema, T.: "Practical Resolution of 3-Phenyl-2H-azirine-2-methanol at Very Low Temperature by Using Lipase Immobilized on Porous Ceramic and Optimized Acylating Agent."Bull.Chem.Soc.Jpn.. 76. 1819-1821 (2003)

Sakai, T.、Matsuda, A.、Korenaga, T.、Ema, T.：“使用固定在多孔陶瓷上的脂肪酶和优化的酰化剂在极低温度下实际拆分 3-苯基-2H-氮丙啶-2-甲醇

Takashi Sakai: "Synthesis of Enantiomerically Pure(R,R)-and(S,S)-1,2-Bis(pentafluorophenyl)ethane-1,2-diamine and Evaluation of the pKa Value by ab initio Calculations"Bulletin of the Chemical Society of Japan. (in press). (2004)

Takashi Sakai：“对映体纯的(R,R)-和(S,S)-1,2-双(五氟苯基)乙烷-1,2-二胺的合成以及从头计算计算pKa值”公告