LIPASE-CATALYZED ASYMMETRIC HYDROLYSIS OF ESTERS HAVING REMOTE CHIRAL PROCHIRAL CENTERS
LIPASE-CATALYZED ASYMMETRIC HYDROLYSIS OF ESTERS HAVING REMOTE CHIRAL PROCHIRAL CENTERS
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DOI：
10.1021/jo00313a010
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发表时间：
1990-12-21
影响因子：
3.6
通讯作者：
GRABOWSKI, EJJ
中科院分区：
文献类型：
--
作者：
HUGHES, DL;BERGAN, JJ;GRABOWSKI, EJJ
当使用市售脂肪酶时，在前手性/手性中心和酯羰基之间具有至多5个键的前手性和外消旋二硫代缩醛酯的酶促水解以至多98%的对映体过量的选择性进行。 对于来自假单胞菌属的脂肪酶，在前手性中心和酯羰基之间具有四个键的底物的化学产率和ee比三键或五键类似物的化学产率和ee更好，这表明选择性不一定随着手性中心和反应位点之间的距离增加而降低。 这些发现是有效的化学酶促合成的两个对映体的一个有效的LTD 4拮抗剂的基石。
Enzymatic hydrolysis of prochiral and racemic dithioacetal esters having up to five bonds between the prochiral/chiral center and the ester carbonyl group proceeds with selectivities up to 98% enantiomeric excess when commercially available lipases are used. For lipase from Pseudomonas sp., chemical yields and ee's were better with the substrate having four bonds between the prochiral center and ester carbonyl than with the three-bond or five-bond analogues, demonstrating that selectivity does not necessarily diminish as the distance between the chiral center and the reaction site increases. These findings are the cornerstone of efficient chemoenzymatic syntheses of both enantiomers of a potent LTD4 antagonist.