Asymmetric Synthesis of Optically Active Natural Products by Lipase-Catalyzed Hydrolysis in Organic Solvent System

有机溶剂体系中脂肪酶催化水解不对称合成光学活性天然产物

• 批准号: 06660139
• 负责人: NAOSHIMA Yoshinobu
• 金额: $ 1.22万
• 依托单位: Okayama University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06660139/
• 关键词: Biocatalyst; Lipase; Bioransformation; Enantioselectivity; Pheromone; Hydrolysis; Asymmetric Synthesis; Enzymatic Reaction; フエロモン; 光学活性天然物

1. We showed that lipase PS-catalyzed hydrolysis displays a higher enantioselectivity in an acetone-water system than in an aqueous system and that the biocatalytic system conyaining acetone could be successfully applied to the chiral synthesis of both the enantiomers of 3-octanol, the pheromone of various species of ants, of (S) 2-tridecanyl acetate and (S) -2-pentadecanyl acetate, the aggregation pheromone components of Drosophila mulleri and D.busckii, and of (R) patulolide A,a macrolide antibiotic isolated from Penicillium urticae S11R59.2. We carried out the enzymatic hydrolysis of the acetates of aliphatic secondary alcohols with lipases PS,AK,and LIP.High enantioselectivity was observed for the lipase PS-catalyzed hydrolysis of (E) -allylic acetate and propargylic acetate in an acetone-water solvent system. In contrast, a decrease in enantio-selectivity was observed for (E) -homoallylic acetate and homopropargylic acetate. The enantioselectivity of lipase LIP (Pseudomonas sp.) was different from that of lipases PS and AK (Pseudomonas sp.).

1。我们表明，与水性系统相比，脂肪酶PS催化的水解在丙酮 - 水系统中显示出更高的对映选择性，并且生物催化系统可以成功地应用于3-粒烯醇和各种物种的甲醇的对照组的手性合成（s）， -2-戊二烷基乙酸，果蝇和d.busckii的聚集信息素成分，以及（R）patulolide A的（R）Patulolide A，一种从弱尿液中分离的大花环抗生素S11R59.2。我们用脂肪酶PS，AK和唇脂进行了脂肪酶次生醇的酶水解。对于脂肪酶PS催化的（E） - 丙酸乙酸乙酸盐和丙烯酸乙酸酯的脂肪酶PS催化的水解，观察到了高的对映选择性。相反，对于（e） - 苯甲酸乙酸酯和同型乙酸酯，观察到对映选择性的降低。脂肪酶唇（假单胞菌sp。）的对映选择性与脂肪酶PS和AK（假单胞菌sp。）不同。

项目成果

Makoto Kamezawa: "Enzymatic Hydrolysis of Alken-and Alkyn-3-ol Acetates in an Acetone-Water Solvent System" Biosci. Biotech. Biochem.59. 549-551 (1995)

Makoto Kamezawa：“丙酮-水溶剂系统中 Alken-和 Alkyn-3-ol 乙酸酯的酶水解”Biosci。

Makoto Kamezawa: "Prearation of Both the Enartiamers of 3-Octard,the Pheromonc of Various Species of Ants,by Enantioselective Hydrolysis wth Pscudomonos cepacia Lipasc" Btosci.Biotech.Biochem.58. 598-599 (1994)

Makoto Kamezawa：“通过对映体选择性水解与洋葱假单胞菌 Lipasc 制备 3-Octard 的两种恩纳蒂姆，即各种蚂蚁的信息素”Btosci.Biotech.Biochem.58。

Makoto Kamezawa: "Preparation of Both the Enantiomers of 3-Octanol, the Pheromone of Various Species of Ants, by Enantioselective Hydrolysis with Pseudomonas cepacia Lipase" Biosci.Biotech.Biochem.58. 598-599 (1994)

Makoto Kamezawa：“通过用洋葱假单胞菌脂肪酶对映选择性水解来制备 3-辛醇（各种蚂蚁的信息素）的两种对映体”Biosci.Biotech.Biochem.58。

Makoto Kamezawa: "Chemoenzymatic Synthesis of (R)-(+)-Patulolide A, a Macrolide Antibiotic Isolated from Penicillium urticae" Liebigs Ann. Chem.(in press). (1996)

Makoto Kamezawa：“(R)-( )-Patulolide A（一种从二斑青霉中分离出的大环内酯抗生素）的化学酶法合成”Liebigs Ann。

Makoto Kamezawa: "Enzymatic Hydrolysis of Alken- and Alkyn-3-ol Acetate in an Acetone-Water Solvent System : Effect of Unsaturation on the Enantioselectivity of Pseudomonas cepacia Lipase-catalyzed Hydrolysis" Biosci.Biotech.Biochem.59. 549-551 (1995)

Makoto Kamezawa：“丙酮-水溶剂系统中 Alken- 和 Alkyn-3-ol 乙酸酯的酶水解：不饱和度对洋葱假单胞菌脂肪酶催化水解对映选择性的影响”Biosci.Biotech.Biochem.59。