Deciphering Pyrrolidine and Olefin Formation Mechanism in Kainic Acid Biosynthesis

Tzu Yu Chen, Shan Xue, Wei Chih Tsai, Tun Cheng Chien, Yisong Guo, Wei Chen Chang

Research output: Contribution to journalArticlepeer-review

Abstract

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.

Original languageEnglish
Pages (from-to)278-282
Number of pages5
JournalACS Catalysis
Volume11
Issue number1
DOIs
Publication statusPublished - 2021 Jan 1

Keywords

  • C-H activation
  • cyclization
  • desaturation
  • enzyme mechanism
  • metalloenzyme

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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