Deciphering Pyrrolidine and Olefin Formation Mechanism in Kainic Acid Biosynthesis
Deciphering Pyrrolidine and Olefin Formation Mechanism in Kainic Acid Biosynthesis
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DOI：
10.1021/acscatal.0c03879
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发表时间：
2021-01-01
期刊：
影响因子：
12.9
通讯作者：
Chang, Wei-chen
中科院分区：
文献类型：
--
作者：
Chen, Tzu-Yu;Xue, Shan;Chang, Wei-chen
金属酶催化的C-H键活化环化反应是天然产物生物合成中构建复杂分子的有效途径。在异软骨藻酸和红藻氨酸的生物合成途径中，单核非血红素铁酶催化环化沿着去饱和反应，该去饱和反应形成吡咯烷和烯烃。使用互补的方法，一个合理的反应途径的红藻氨酸形成的建立。在通过Fe（IV）-氧代物种提取H原子之后，所产生的自由基与N-异戊二烯基相互作用以促进吡咯烷安装。然后，该反应经历碳阳离子触发的去饱和以构建红藻氨酸。
Metalloenzyme-catalyzed cyclization involving C-H bond activation is a powerful strategy to construct molecular complexity found in natural product biosynthesis. In the isodomoic acid and kainic acid biosynthetic pathways, mononuclear non-heme iron enzymes catalyze cyclization along with desaturation reactions that install the pyrrolidine and the olefin. Using complementary approaches, a plausible reaction pathway of kainic acid formation is established. Following H atom abstraction by an Fe(IV)-oxo species, the resulting radical interacts with the N-prenyl group to promote pyrrolidine installation. The reaction then undergoes a carbocation-triggered desaturation to construct kainic acid.