Taspinar, Oemer, Wilczek, Tobias, Erver, Julian, Breugst, Martin ORCID: 0000-0003-0950-8858, Neudoerfl, Joerg-Martin and Schmalz, Hans-Guenther ORCID: 0000-0003-0489-1827 (2020). Synthesis of the 8,19-Epoxysteroid Eurysterol A. Chem.-Eur. J., 26 (19). S. 4256 - 4261. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3765

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Abstract

We report the first chemical synthesis of eurysterol A, a cytotoxic and antifungal marine steroidal sulfate with a unique C8-C19 oxy-bridged cholestane skeleton. After C19 hydroxylation of cholesteryl acetate, used as an inexpensive commercial starting material, the challenging oxidative functionalization of ring B was achieved by two different routes to set up a 5 alpha-hydroxy-7-en-6-one moiety. As a key step, an intramolecular oxa-Michael addition was exploited to close the oxy-bridge (8 beta,19-epoxy unit). DFT calculations show this reversible transformation being exergonic by about -30 kJ mol(-1). Along the optimized (scalable) synthetic sequence, the target natural product was obtained in only 11 steps in 5 % overall yield. In addition, an access to (isomeric) 7 beta,19-epoxy steroids with a previously unknown pentacyclic ring system was discovered.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Taspinar, OemerUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Wilczek, TobiasUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Erver, JulianUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Breugst, MartinUNSPECIFIEDorcid.org/0000-0003-0950-8858UNSPECIFIED
Neudoerfl, Joerg-MartinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Schmalz, Hans-GuentherUNSPECIFIEDorcid.org/0000-0003-0489-1827UNSPECIFIED
URN: urn:nbn:de:hbz:38-339305
DOI: 10.1002/chem.202000585
Journal or Publication Title: Chem.-Eur. J.
Volume: 26
Number: 19
Page Range: S. 4256 - 4261
Date: 2020
Publisher: WILEY-V C H VERLAG GMBH
Place of Publication: WEINHEIM
ISSN: 1521-3765
Language: English
Faculty: Faculty of Mathematics and Natural Sciences
Divisions: Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
MARINE NATURAL-PRODUCTS; INTRAMOLECULAR HYDROGEN ABSTRACTION; DESS-MARTIN PERIODINANE; OXA-MICHAEL REACTION; CARBON DOUBLE-BONDS; CATALYZED DIHYDROXYLATION; STEREOSELECTIVE-SYNTHESIS; POLYOXYGENATED STEROIDS; SECONDARY ALCOHOLS; IODINE(V) REAGENTSMultiple languages
Chemistry, MultidisciplinaryMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/33930

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