Shiina Tetsuya, Ozaki Taro, Matsu Yusuke, Nagamine Shota, Liu Chengwei, Hashimoto Masaru, Minami Atsushi, Oikawa Hideaki
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Faculty of Agriculture and Life Science, Hirosaki University, Hirosaki 036-8561, Japan.
Org Lett. 2020 Mar 6;22(5):1997-2001. doi: 10.1021/acs.orglett.0c00340. Epub 2020 Feb 17.
To elucidate the biosynthesis of a fungicidal dimeric anhydride zopfiellin, the putative biosynthetic gene cluster was identified. We conducted heterologous expression of candidate genes for the synthesis of maleic anhydride and its dimerization and identified the two isomeric dimers with 9-membered rings as products. Notably, α-ketoglutarate-dependent dioxygenase ZopK oxidized one of the dimers, giving the 8-membered ring of zopfiellin. The mechanism of oxidative rearrangement is proposed by analyzing the incorporation of C-labeled precursors.
为了阐明杀真菌二聚酸酐佐菲菌素的生物合成过程，我们鉴定了其假定的生物合成基因簇。我们对合成马来酸酐及其二聚化的候选基因进行了异源表达，并鉴定出两种具有九元环的异构二聚体作为产物。值得注意的是，依赖α-酮戊二酸的双加氧酶ZopK氧化了其中一种二聚体，形成了佐菲菌素的八元环。通过分析C标记前体的掺入情况，我们提出了氧化重排的机制。
