Chemoenzymatic oxygenation method for sesquiterupenoid synthesis based on Fe-chelate and ferric-chelate reductase
Chemoenzymatic oxygenation method for sesquiterupenoid synthesis based on Fe-chelate and ferric-chelate reductase
复制标题
基于铁螯合物和铁螯合物还原酶的化学酶氧化法合成倍半萜类化合物
DOI：
10.1080/09168451.2019.1707062
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Mio Kubota and Kuniki Kino
中科院分区：
文献类型：
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作者：
Satoru Umezawa;Hiroko Akao;Mio Kubota and Kuniki Kino
倍半萜类化合物是天然化合物中种类最多的一类，具有多种化学结构和生物活性。在我们之前的工作中，我们开发了基于Fe（II）-EDTA和铁螯合还原酶的组合的化学酶促氧化方法，该方法可以合成（-）-罗通酮，黑胡椒的一种关键芳香倍半萜。Fe（II）-EDTA催化倍半萜氧化生成倍半萜类化合物，Fe（II）-EDTA还原酶催化Fe（II）-EDTA的补充和再生。然后，我们研究了各种Fe 2+螯合物对倍半萜烯催化氧化的影响，并将此系统应用于气味倍半萜烯类化合物的合成。我们确定Fe（II）-NTA是一个有效的氧化催化剂的筛选方法，侧重于配体结构和配位原子的Fe 2 +-螯合物。有价值的气味倍半萜类化合物，如（+）-诺卡酮、（-）-异长叶烯酮和（-）-β-香叶烯氧化物，分别以66%、82%和67%的摩尔转化率从每种前体倍半萜氧化合成。三（2-吡啶甲基）胺; GlcDH：葡萄糖脱氢酶; HP-β-CD：羟丙基-β-环糊精
Sesquiterpenoids are one of the most diverse groups in natural compounds with various chemical structures and bioactivities. In our previous work, we developed the chemoenzymatic oxygenation method based on the combination of Fe(II)-EDTA and ferric-chelate reductase that could synthesize (−)-rotundone, a key aroma sesquiterpenoid of black pepper. Fe(II)-EDTA catalyzed the oxygenation of sesquiterpene to sesquiterpenoid, and ferric-chelate reductase catalyzed the supply and regeneration of Fe(II)-EDTA in this system. We then investigated the effect of various Fe2+-chelates on the catalytic oxygenation of sesquiterpene and applied this system to the synthesis of odor sesquiterpenoids. We determined Fe(II)-NTA to be an efficient oxygenation catalyst by the screening approach focusing on ligand structures and coordination atoms of Fe2+-chelates. Valuable odor sesquiterpenoids such as (+)-nootkatone, (−)-isolongifolenone, and (−)-β-caryophyllene oxide were oxygenatively synthesized from each precursor sesquiterpene by 66%, 82%, and 67% of the molar conversion rate, respectively.Abbreviations:EDTA: ethylenediaminetetraacetate; NTA: nitrilotriacetate; DTPA: diethylenetriaminepentaacetate; phen:o-phenanthroline; cyclam: 1,4,8,11-tetraazacyclotetradecane; TPA: tris(2-pyridylmethyl)amine; GlcDH: glucose dehydrogenase; HP-β-CD: hydroxypropyl-β-cyclodextrin