Navigating the Landscape of Cycloartanyl Cations: Synthesis of Fortunefuroic Acid I, Parkeol, 25,26,27-Trinor-3α-hydroxy-17,13-friedolanosta-8,12-dien-23-one, and Spirochensilide A

Verfasst von

Manuel Georgio Klaus Kizakis, Marvin Treger, Gerald Dräger, Carolin König, Philipp Heretsch

Abstract

For the semisynthesis of plant-derived triterpenoid natural products, access to cycloartenol or a derivative is mandatory. We here describe a robust access from the renewable feedstock γ-oryzanol and isolation by differentiable reactivity. Using either radical-polar crossover or polar modes of activation, we then selectively access different carbenium ions and elucidate their fate in rearrangements. As a result, a chemical toolbox for the modular and stepwise skeletal rearrangement to access natural products with increasing levels of divergence from the parent cycloartane is reported. Using this toolbox, parkeol-, 17,13-friedocycloartane-, 17,13-friedoparkeol-, as well as 17,13- and 17,14-friedolanostane systems are selectively obtained and transformed via short routes to the plant metabolites parkeol (3), fortunefuroic acid I (4), 25,26,27-trinor-3α-hydroxy-17,13-friedolanosta-8,12-dien-23-one (“sibiricanone”, 5), and spirochensilide A (6). Probing the innate reactivity of cycloartanyl cations and corroborating the experimental results with DFT calculations sheds light on the potential biogenesis of these and related plant metabolites and, thus, can account for the occurrence of 17,14-friedolanostanes in plants.

Details

Organisationseinheit(en): Institut für Organische Chemie
AG Naturstoffsynthese
Institut für Physikalische Chemie und Elektrochemie
AG Computational Chemistry
PhoenixD: Simulation, Fabrikation und Anwendung optischer Systeme
AG Synthetische Chemie
Abteilung für Massenspektrometrie
Typ: Artikel
Journal: Journal of the American Chemical Society
Band: 148
Seiten: 13912-13920
Anzahl der Seiten: 9
ISSN: 0002-7863
Publikationsdatum: 08.04.2026
Publikationsstatus: Veröffentlicht
Peer-reviewed: Ja
Ziele für nachhaltige Entwicklung: SDG 7 - Erschwingliche und saubere Energie
Elektronische Version(en): https://doi.org/10.1021/jacs.5c22292 (Zugang: Offen )