Kourgiantaki Maria, Zografos Alexandros L
Laboratory of Organic Chemistry, Department of Chemistry, Aristotle University of Thessaloniki, Main University Campus, 54124 Thessaloniki, Greece.
Org Lett. 2025 May 23;27(20):5039-5043. doi: 10.1021/acs.orglett.5c00485. Epub 2025 May 13.
The biosynthetic pathways leading to pseudoguaianolides and seco-guaianolides remain unclear. In this work, we demonstrate that highly oxidized 8,12-guaianolides serve as unprecedented precursors, enabling chemoselective, one-step access to pseudoguaianolide, seco-guaianolide, and xanthanolide-type sesquiterpenoids. Key mechanistic insights reveal the pivotal role of peroxide substituents on the guaianolide core and stereoelectronic factors in controlling reaction outcomes. These findings shed light on guaianolide selectivity and may mirror actual biosynthetic pathways, offering transformative potential for oxidative transformations in sesquiterpenoid synthesis.
导致伪愈创木内酯和裂环愈创木内酯的生物合成途径仍不清楚。在这项工作中，我们证明了高度氧化的8,12-愈创木内酯可作为前所未有的前体，实现对伪愈创木内酯、裂环愈创木内酯和黄原内酯型倍半萜的化学选择性一步合成。关键的机理见解揭示了过氧化物取代基在愈创木内酯核心上的关键作用以及立体电子因素对反应结果的控制。这些发现揭示了愈创木内酯的选择性，并可能反映实际的生物合成途径，为倍半萜合成中的氧化转化提供了变革潜力。
