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Formal Semisynthesis of Demethylgorgosterol Utilizing a Stereoselective Intermolecular Cyclopropanation Reaction

Rosenbaum, Nicolai 1; Schmidt, Lisa 1; Mohr, Florian 1; Fuhr, Olaf 2; Nieger, Martin; Bräse, Stefan 1
1 Institut für Organische Chemie (IOC), Karlsruher Institut für Technologie (KIT)
2 Karlsruhe Nano Micro Facility (KNMF), Karlsruher Institut für Technologie (KIT)

Abstract:

In this study, we report a convenient and high yielding formal semisynthesis of demethylgorgosterol, a marine steroid with an intriguing sidechain containing a cyclopropane unit. This was achieved through the synthesis of an advanced ketone intermediate. The synthetic route features a total of ten steps, starting from commercially available stigmasterol, with an overall yield of 27 %. The key step was a stereoselective intermolecular cyclopropanation reaction. This reaction proceeded in 82 % yield, the resulting cyclopropane carboxylic ester shows a trans/cis ratio of 89 : 11, with a diastereomeric ratio for the trans-diastereomers of >99 : 1. A reduction/oxidation sequence afforded the corresponding aldehyde, which was used in a Grignard reaction. A final oxidation step then yielded the desired ketone. This novel route presents a platform to further investigate the medicinal applications of gorgosterol-type steroids and to fully understand their role in coral symbiosis.


Verlagsausgabe §
DOI: 10.5445/IR/1000135337
Veröffentlicht am 14.07.2021
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Biologische und Chemische Systeme (IBCS)
Institut für Nanotechnologie (INT)
Institut für Organische Chemie (IOC)
Karlsruhe Nano Micro Facility (KNMF)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 12.03.2021
Sprache Englisch
Identifikator ISSN: 1434-193X, 1099-0690
KITopen-ID: 1000135337
HGF-Programm 43.33.11 (POF IV, LK 01) Adaptive and Bioinstructive Materials Systems
Weitere HGF-Programme 43.32.01 (POF IV, LK 01) Molecular Materials Basis for Optics & Photonics
Erschienen in European journal of organic chemistry
Verlag John Wiley and Sons
Band 2021
Heft 10
Seiten 1568–1574
Vorab online veröffentlicht am 23.01.2021
Nachgewiesen in Web of Science
Dimensions
Scopus
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