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)开发在极低温度下具有固定化脂肪酶的高效和对映选择性催化体系。(a)为了开发固定化脂肪酶，我们研究了涂覆在多孔陶瓷载体上的有机桥。有机桥通过共价键与多孔陶瓷结合。当含有异丁酸酯部分的有机桥用于脂肪酶催化拆分外消旋醇时，固定化脂肪酶在-30℃下的对映选择性和催化活性均得到显着增强。(b)为了进一步提高固定化脂肪酶的效率，我们对酰化剂进行了优化。当使用丁酸乙烯酯作为酰化剂时，在-40℃时对映选择性和催化活性均达到最大。(2)光学活性氟化胺的开发及其在超分子材料中的应用。(a)通过脂肪酶催化拆分得到对映体纯的含五氟苯基的氰醇。以手性氰醇为原料合成了新型对映体纯的含有五氟苯基和苯基的1,2-氨基醇。化合物的X射线分析表明五氟苯基与醇氧原子之间存在相互作用。这种相互作用为超分子材料的设计提供了新的有用信息。(b)通过亚氨基-频哪醇偶联反应合成了新型对映体纯的含五氟苯基的1,2-二胺。由于五氟苯基的强吸电子能力，与非氟化衍生物相比，二胺的碱性降低。事实表明五氟苯基对氮原子的影响。

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

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

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，