Regioselective hydroxylation of diverse flavonoids by an aromatic peroxygenase
Regioselective hydroxylation of diverse flavonoids by an aromatic peroxygenase
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DOI：
10.1016/j.tet.2011.05.008
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发表时间：
2011-07-01
期刊：
影响因子：
2.1
通讯作者：
Hofrichter, Martin
中科院分区：
文献类型：
--
作者：
Barkova, Katerina;Kinne, Matthias;Hofrichter, Martin
芳香族过氧合酶是一种选择性氧化多种有机化合物的胞外真菌生物催化剂。我们发现，真菌茶树菇（AaeAPO）的过氧合酶催化H2 O2依赖的不同黄酮类化合物的羟基化。反应快速进行并区域选择性地优先产生单羟基化产物，例如，从黄烷酮、芹菜素、毛地黄黄酮、黄酮以及大豆苷元、槲皮素、山奈酚、染料木黄酮中提取。除了羟基化，完全甲氧基化的柑橘素的O-脱甲基被AaeAPO催化。该酶仅对槲皮素糖苷芦丁缺乏活性，可能是由于大体积糖取代基的空间位阻。机理研究表明，在羟基化和H2 O2衍生的氧纳入反应产物的环氧中间体的存在下。我们的研究结果提出了真菌过氧合酶可能是有用的多功能，成本效益高，可扩展的类黄酮代谢产物的合成的可能性。(C)2011爱思唯尔有限公司保留所有权利。
Aromatic peroxygenases are extracellular fungal biocatalysts that selectively oxidize a variety of organic compounds. We found that the peroxygenase of the fungus Agrocybe aegerita (AaeAPO) catalyzes the H2O2-dependent hydroxylation of diverse flavonoids. The reactions proceeded rapidly and regioselectively yielding preferentially monohydroxylated products, e.g., from flavanone, apigenin, luteolin, flavone as well as daidzein, quercetin, kaempferol, and genistein. In addition to hydroxylation, O-demethylation of fully methoxylated tangeretin was catalyzed by AaeAPO. The enzyme was merely lacking activity on the quercetin glycoside rutin, maybe due to sterical hindrance by the bulky sugar substituents. Mechanistic studies indicated the presence of epoxide intermediates during hydroxylation and incorporation of H2O2-derived oxygen into the reaction products. Our results raise the possibility that fungal peroxygenases may be useful for versatile, cost-effective, and scalable syntheses of flavonoid metabolites. (C) 2011 Elsevier Ltd. All rights reserved.