Universität zu Köln

Baars, Julian, Grimm, Isabelle ORCID: 0000-0001-7688-4760, Blunk, Dirk ORCID: 0000-0001-6365-0404, Neudoerfl, Joerg-Martin and Schmalz, Hans-Guenther ORCID: 0000-0003-0489-1827 (2021). Enantioselective Total Synthesis and Structural Revision of Dysiherbol A. Angew. Chem.-Int. Edit., 60 (27). S. 14915 - 14921. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3773

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Abstract

A 12-step total synthesis of the natural product dysiherbol A, a strongly anti-inflammatory and anti-tumor avarane meroterpene isolated from the marine sponge Dysidea sp., was elaborated. As key steps, the synthesis features an enantioselective Cu-catalyzed 1,4-addition/enolate-trapping opening move, an Au-catalyzed double cyclization to build up the tetracyclic core-carbon skeleton, and a late installation of the C5-bridgehead methyl group via proton-induced cyclopropane opening associated with spontaneous cyclic ether formation. The obtained pentacyclic compound (corresponding to an anhydride of the originally suggested structure for dysiherbol A) showed identical spectroscopic data as the natural product, but an opposite molecular rotation. CD-spectroscopic measurements finally confirmed that both the constitution and the absolute configuration of the originally proposed structure of (+)-dysiherbol A need to be revised.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Baars, Julian UNSPECIFIED UNSPECIFIED UNSPECIFIED Grimm, Isabelle UNSPECIFIED orcid.org/0000-0001-7688-4760 UNSPECIFIED Blunk, Dirk UNSPECIFIED orcid.org/0000-0001-6365-0404 UNSPECIFIED Neudoerfl, Joerg-Martin UNSPECIFIED UNSPECIFIED UNSPECIFIED Schmalz, Hans-Guenther UNSPECIFIED orcid.org/0000-0003-0489-1827 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-564907
DOI:	10.1002/anie.202105733
Journal or Publication Title:	Angew. Chem.-Int. Edit.
Volume:	60
Number:	27
Page Range:	S. 14915 - 14921
Date:	2021
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3773
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language REAGENTS; AVAROL; CYCLIZATION; CONSTRUCTION; MEROTERPENES; (+)-AVARONE; DERIVATIVES; STACHYFLIN; REACTIVITY; INHIBITORS Multiple languages Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/56490