The biosynthesis of acarbose and validamycin
The biosynthesis of acarbose and validamycin
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DOI：
10.1002/tcr.1015
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发表时间：
2001-01-01
期刊：
影响因子：
6.6
通讯作者：
Floss, HG
中科院分区：
文献类型：
--
作者：
Mahmud, T;Lee, S;Floss, HG
本文报道的研究已经建立了阿卡波糖和井冈霉素的mC（7）N单元从景天庚酮糖7-磷酸的生物合成来源，并已确定2-epi-5-epi-valiolone为初始环化产物。阿卡波糖的脱氧己糖部分来自葡萄糖，脱氧胸苷基-二磷酸-4-酮-6-脱氧-D-葡萄糖（dTDP-4-酮-6-脱氧-D-葡萄糖）作为近似中间体。然而，尽管阿卡波糖和缬克拉霉素A中氨基环醇部分的来源相同，但它们的形成途径似乎有很大不同。井冈霉素A的形成涉及许多离散的酮环醇中间体，5-epi-valiolone，valienone，和validone，而没有游离的中间体已被确定的途径，从2-epi-5-epivaliolone阿卡波糖的假二糖部分。现在的阶段是解开阿卡波糖和井冈霉素的假二糖部分的两个组分通过氮桥彼此独特偶联的机制。(C)2001年日本化学杂志论坛和John Wiley Sons，Inc.
The studies reported here have established the biosynthetic origin of the mC(7)N units of acarbose and validamycin from sedo-heptulose 7-phosphate, and have identified 2-epi-5-epi-valiolone as the initial cyclization product. The deoxyhexose moiety of acarbose arises from glucose with deoxythymidyl-diphospho-4-keto-6-deoxy-D-glucose (dTDP-4-keto-6-deoxy-D-glucose) as a proximate intermediate. However, despite the identical origin of the aminocyclitol moieties in acarbose and valiclamycin A, the pathways of their formation seem to be substantially different. Validamycin A formation involves a number of discrete ketocyclitol intermediates, 5-epi-valiolone, valienone, and validone, whereas no free intermediates have been identified on the pathway from 2-epi-5-epivaliolone to the pseudodisaccharide moiety of acarbose. The stage is now set for unraveling the mechanism or mechanisms by which the two components of the pseudodisaccharide moieties of acarbose and validamycin are uniquely coupled to each other via a nitrogen bridge. (C) 2001 The Japan Chemical Journal Forum and John Wiley Sons, Inc.