2025-08-19 デラウェア大学 (UD)
<関連情報>
- https://www.udel.edu/udaily/2025/august/chemistry-method-liver-cancer-william-chain-cas/
- https://onlinelibrary.wiley.com/doi/abs/10.1002/ange.202506537
(–)-Psiguadial Aのエナンチオ選択的全合成 Enantioselective Total Synthesis of (–)-Psiguadial A
Liam P. O’Grady, Marcel Achtenhagen, Michael F. Wisthoff, Robert S. Lewis, Katarina Pfeifer, Weifeng Zheng, Maxwell I. Martin, Glenn P. A. Yap, William J. Chain
Angewandte Chemie Published: 20 May 2025
DOI:https://doi.org/10.1002/ange.202506537
Abstract
The first enantioselective total synthesis of the antiproliferative natural product (–)-psiguadial A is reported. This approach features the enantioselective synthesis of a complex tricyclic terpenoid precursor, the union of that precursor with a polyketide component by an enolate-ortho-quinone methide coupling reaction to form a highly congested carbon─carbon bond, and an acid-mediated intramolecular hydration ring-closure leveraging a fully substituted alkene to generate the unique oxepane core structure of the natural product.
Graphical Abstract
A biomimetic approach harnessing reactive species enabled the enantioselective synthesis of the complex meroterpenoid psiguadial A through an enolate–ortho-quinone methide (oQM) umpolung strategy and late-stage cationic ring closure. The final fully decorated aromatic core was successfully synthesized by adaptation of modern aryl methyl ether deprotection and formylation methodologies, establishing efficient access to this class of natural products.
