Vicinal Bis(methylene) Heterocyclic Diene in Natural Product Synthesis: A Convergent Biomimetic Total Synthesis of Prunolactone A
The first total syntheses of the natural isocoumarin prunolactone A with a 6/6/6/6/6 spiropentacyclic skeleton and its unnatural (3'<i>R</i>)-epimer in 10 and 8 steps, respectively, are reported. The syntheses feature <i>in situ</i> generation of a reactive 3,4-bis(methylene)isocoumarin intermediate, its biomimetic Diels-Alder reactions with the shikimic-acid-derived scytolide and (8<i>R</i>)-scytolide, and a Mitsunobu reaction allowing access to scytolide in a stereochemically pure form. Computational support for the selectivity of the Diels-Alder reaction is provided.
Authors
- Milan Pour (ORCID: https://orcid.org/0000-0002-3962-7922)
- Lucie Nováková (ORCID: https://orcid.org/0000-0003-3570-5871)
- Petr Matouš (ORCID: https://orcid.org/0000-0002-1617-1168)
- Martina Bonsignore (ORCID: https://orcid.org/0000-0001-6611-2150)
- Erik Andris (ORCID: https://orcid.org/0000-0002-9336-0157)
- Zdeňka Růžičková (ORCID: https://orcid.org/0000-0003-0259-5557)
- Jiřı́ Kuneš
- Michal Kadaník (ORCID: https://orcid.org/0000-0001-9148-153X)
- Ekaterina Frantsuzova
Institutions
- University of Pardubice (CZ)
- Charles University (CZ)
- Czech Academy of Sciences, Institute of Organic Chemistry and Biochemistry (CZ)
Publication Details
- Journal
- Organic Letters
- Published
- 2024-12-07
- DOI
- https://doi.org/10.1021/acs.orglett.4c04378
- Citations
- 2
- Primary Topic
- Synthetic Organic Chemistry Methods
- Type
- article
- Field-Weighted Citation Impact
- 0.50
Funders
- Univerzita Karlova v Praze
- European Commission
- Ministerstvo Školství, Mládeže a Tělovýchovy
- Grantová Agentura České Republiky
- Masarykova Univerzita