Universität zu Köln

Schwamborn, Marvin ORCID: 0009-0002-8621-8838, Stremmel, Linus, Neudörfl, Jörg‐Martin ORCID: 0000-0002-2918-0565 and Schmalz, Hans‐Günther ORCID: 0000-0003-0489-1827 (2025). Structural Revision and Total Synthesis of Primarolides A and B via Massarinin A as a Common Precursor – Discovery of a Surprising 1,4‐Aryl Shift. Chemistry – A European Journal, 31 (18). pp. 1-8. Wiley. ISSN 0947-6539

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Abstract

[Artikel-Nr. e202404408] To probe the possible non‐enzymatic formation of the polyketidic fungal metabolites primarolides A and B, the supposed 2‐formyl‐benzophenone precursor was prepared by chemical synthesis exploiting an anionic homo‐Fries rearrangement to set up the highly substituted benzophenone unit. Conversion of this compound into the putative primarolides (i. e. the isomeric phthalide and the corresponding N ‐phenyl‐isoindolinone) revealed that the proposed structures had to be revised. Subsequently, the natural product massarinin A, which displays a similar 2‐formyl‐benzophenone substructure, was synthesized following a related strategy. Treatment of massarinin A with Sc(OTf) 3 or cyanide as a nucleophilic catalyst unexpectedly proceeded under 1,4‐aryl migration to afford primarolide A. In contrast, reaction of massarinin A with aniline gave rise to primarolide B without aryl shift. All structural assignments were confirmed by X‐ray crystal analysis and the proposed mechanism of the skeletal rearrangement was supported by 13 C labeling. The study not only led to the total synthesis and structural revision of the primarolides but also supports the hypothesis of their non‐enzymatic formation as racemates under the reported fermentation conditions, with the added suberoylanilide hydroxamic acid (SAHA) likely serving as the source of aniline.

Item Type:	Article
Creators:	Creators Email ORCID ORCID Put Code Schwamborn, Marvin UNSPECIFIED https://orcid.org/0009-0002-8621-8838 UNSPECIFIED Stremmel, Linus UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudörfl, Jörg‐Martin UNSPECIFIED https://orcid.org/0000-0002-2918-0565 UNSPECIFIED Schmalz, Hans‐Günther UNSPECIFIED https://orcid.org/0000-0003-0489-1827 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-797140
Identification Number:	10.1002/chem.202404408
Journal or Publication Title:	Chemistry – A European Journal
Volume:	31
Number:	18
Page Range:	pp. 1-8
Date:	25 March 2025
Publisher:	Wiley
ISSN:	0947-6539
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	Chemistry and allied sciences
['eprint_fieldname_oa_funders' not defined]:	Publikationsfonds UzK
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/79714