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<p>Monoterpene indole alkaloids (MIAs) constitute one of the largest and most structurally diverse classes of plant specialized metabolites, with over 3000 members identified to date. Their low natural abundance, as well as exceptional structural complexity and stereochemical richness, presents major challenges for chemical synthesis and has driven decades of research into their biosynthesis. Since the near-complete elucidation of the iconic anticancer alkaloid vinblastine biosynthetic pathway in 2018, numerous additional MIA biosynthetic pathways and catalytic mechanistic studies have provided critical insights into MIA metabolism. This review aims to provide readers with a concise yet comprehensive reference to recent advances in the field. We summarize progress (2016–2026) in understanding the secoiridoid pathway, which provides the monoterpenoid precursor to MIAs, as well as the downstream alkaloid biosynthetic networks and tailoring reactions responsible for their remarkable chemical diversity. The biosynthetic pathways of representative MIAs, including vinblastine, strychnine, ajmaline, and quinine, are discussed to illustrate key mechanistic features. Remarkably, cinnamyl alcohol dehydrogenase-like reductases, a distinct feature of MIA biosynthesis compared with other major classes of plant metabolites, together with cytochrome P450 monooxygenases, and α/β-hydrolase-type cyclases play key roles in scaffold formation and diversification. This review also highlights the emerging importance of these enzyme classes in shaping MIA chemical diversity. Together, these advances have enabled increasingly complete biosynthetic frameworks for major MIA classes and have laid the foundation for their partial or complete reconstruction in heterologous systems through synthetic biology.</p>

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Biosynthesis of monoterpenoid indole alkaloids and selected updates on their metabolic engineering

  • 期刊论文

  • 发表日期：

    2026年7月20日

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  • Negar Khorshidi,
  • Yang Qu

摘要

Monoterpene indole alkaloids (MIAs) constitute one of the largest and most structurally diverse classes of plant specialized metabolites, with over 3000 members identified to date. Their low natural abundance, as well as exceptional structural complexity and stereochemical richness, presents major challenges for chemical synthesis and has driven decades of research into their biosynthesis. Since the near-complete elucidation of the iconic anticancer alkaloid vinblastine biosynthetic pathway in 2018, numerous additional MIA biosynthetic pathways and catalytic mechanistic studies have provided critical insights into MIA metabolism. This review aims to provide readers with a concise yet comprehensive reference to recent advances in the field. We summarize progress (2016–2026) in understanding the secoiridoid pathway, which provides the monoterpenoid precursor to MIAs, as well as the downstream alkaloid biosynthetic networks and tailoring reactions responsible for their remarkable chemical diversity. The biosynthetic pathways of representative MIAs, including vinblastine, strychnine, ajmaline, and quinine, are discussed to illustrate key mechanistic features. Remarkably, cinnamyl alcohol dehydrogenase-like reductases, a distinct feature of MIA biosynthesis compared with other major classes of plant metabolites, together with cytochrome P450 monooxygenases, and α/β-hydrolase-type cyclases play key roles in scaffold formation and diversification. This review also highlights the emerging importance of these enzyme classes in shaping MIA chemical diversity. Together, these advances have enabled increasingly complete biosynthetic frameworks for major MIA classes and have laid the foundation for their partial or complete reconstruction in heterologous systems through synthetic biology.