New Development of Enzyme Utilization in Organic Solvents

有机溶剂中酶利用的新进展

• 批准号: 04806019
• 负责人: YAMAMOTO Yukio
• 金额: $ 1.28万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04806019/
• 关键词: Lipase; beta-Lactone; Molecular transformation; Optically active compound; メバロノラクトン; シリルケテン

By the catalytic action of a lipase, Saiken 100, primary, secondary, and tertiary alcohols were effectively acylated with trimethylsilylketene in organic media, to give trimethylsilylacetyl esters. The enzyme also successfully acylated a phenol and bulky alcohols as well as a substrate bearing a carboxyl group. The acylation with triethylsilylketene and dimethylphenylsilylketene was also catalyzed by the enzyme.Diketene having a highly strained 4-membered ring and intramolecular enol-ester structure was found to be a powerful acylating agent for lipase mediate acylation of alcohols in organic solvents. The stereoselectivity with a lipase, Amano PS,was extremely high which denied the conventional propose of the catalysis on the protein surface. The remaining alcohols and generated esters were able to be separated easily by simple fractional distilllation. beta-Lactones having the similar structure was also trans-esterified with ring opening stereoselectively which were very important starting materials for natural products synthesis and bio-degradable copolymers.

在脂肪酶Saiken 100的催化作用下，伯、仲、叔醇与三甲基硅基乙烯酮在有机介质中有效地酰化，得到三甲基硅基乙酰酯。该酶还成功地酰化了苯酚和大体积醇以及带有羧基的底物。该酶还能催化三乙基硅基乙烯酮和二甲基苯基硅基乙烯酮的酰化反应，双乙烯酮具有高张力的四元环和分子内烯醇酯结构，是脂肪酶催化醇在有机溶剂中酰化反应的强酰化剂。脂肪酶Amano PS的立体选择性极高，否定了传统的蛋白质表面催化的设想。剩余的醇和生成的酯能够通过简单的分馏容易地分离。具有类似结构的β-内酯也可以立体选择性地进行酯交换开环，这是天然产物合成和生物降解共聚物的非常重要的起始原料。

项目成果

沢田 誠二: "Kinelics of Thermostable Alanine Racemase of Bacillus stearothermophlus" Biosci Biotech Biochem. 58. 807-811 (1994)

Seiji Sawada：“嗜热脂肪芽孢杆菌的热稳定性丙氨酸消旋酶的动力学”Biosci Biotech Biochem 58. 807-811 (1994)

星野 淳一: "Fauilc Synthesis of ^<13>C-2- Batenedinitrile and Regiospecifically Labeled ^<13>C,^<15>N-Pyridoxines" Biosci Biotech Biochem. 58. 1939-1941 (1994)

Junichi Hoshino：“^ 13 C-2-巴特烯腈和区域特异性标记的^ 13 C，^ 15 N-吡哆醇的失败合成”Biosci Biotech Biochem。58。1939-1941（1994）

Rui Tamura: "Asymmetric Synthesis of Clavularia A" J.Org.Chem. 58. 4471-4472 (1993)

Rui Tamura：“Clavularia A 的不对称合成”J.Org.Chem。

S.Sawada: "Kinetics of Thermos table Aladdin Racemes of Bacillus stearothermophilus" Bionics. Biotic. Biochem.58. 807-811 (1994)

S.Sawada：“嗜热脂肪芽孢杆菌的热水瓶表阿拉丁总状体的动力学”仿生学。

J.Hoshino: "Facile Synthesis of ^<13>C-2-Butenedinitrile and Regiospecifically Labeled ^<13>C,^<15>N-Pyridoxines." Bionics. Biotic. Biochem.58. 1939-1941 (1994)

J.Hoshino：“^ 13 C-2-丁烯二腈和区域特异性标记的^ 13 C，^ 15 N-吡哆醇的简便合成。”