Document type
ArticleVersion
Accepted versionPublication date
Publication license
Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/193700
Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings
Journal Title
Director/Tutor
Additional contribution
Journal ISSN
Volume Title
Abstract
In previous work we reported the formal synthesis of the marine macrolide (−)-callyspongiolide through a synthetic approach in which the generation of the key macrocyclic core relies on a ruthenium-catalyzed ring-closing metathesis reaction. However, besides the predicted macrolactone intermediate, an undesired cyclooctene was observed. We investigate here the mechanism of this critical step through density functional theory calculations. The results indicate that the chemoselectivity is not under kinetic control but ruled by thermodynamics. This conclusion is further confirmed by additional experimental studies.
Related resource
Subject (English)
Citation
Citation
DÍAZ-RUIZ, Marina, et al. Origin of the selectivity in the ring-closing metathesis step of the synthesis of (−)-callyspongiolide: Formation of fourteen-versus eight-membered rings. Tetrahedron. 2022. ISSN 0040-4020. [consulted: 9 of October of 2026]. Available at: https://hdl.handle.net/2445/193700