Division of Chemistry, Graduate School of Science, Hokkaido University , Sapporo 060-0810, Japan.
Graduate School of Engineering, Hokkaido University , Sapporo 060-8628, Japan.
Org Lett. 2016 Oct 7;18(19):5026-5029. doi: 10.1021/acs.orglett.6b02482. Epub 2016 Sep 15.
The late-stage biosynthetic pathway of the indole diterpene shearinine involving four enzymatic reactions (JanQDOJ) was elucidated by an efficient heterologous expression system using Aspergillus oryzae. Key oxidative cyclization, forming a characteristic A/B bicyclic shearinine core by flavoprotein oxidase, was studied using a substrate analogue and a buffer containing HO. These experimental data provided evidence that JanO catalyzes two-step oxidation via a hydroxylated product and that the JanO reaction involves the hydride-transfer mechanism.
通过使用米曲霉的高效异源表达系统，阐明了吲哚二萜雪灵芝素的晚期生物合成途径涉及四个酶促反应（JanQDOJ）。使用底物类似物和含有 HO 的缓冲液研究了关键的氧化环化反应，通过黄素蛋白氧化酶形成特征性的 A/B 双环雪灵芝素核心。这些实验数据提供了证据表明 JanO 通过羟化产物催化两步氧化，并且 JanO 反应涉及氢转移机制。
