Total Synthesis of (+)-Erogorgiaene and the Pseudopterosin A-F Aglycone via Enantioselective Cobalt-Catalyzed Hydrovinylation.

Autor: Movahhed S; University of Cologne, Greinstrasse 4, 50939, Koeln, Germany., Westphal J; University of Cologne, Greinstrasse 4, 50939, Koeln, Germany., Kempa A; TH Köln, Faculty of Applied Natural Sciences, Kaiser-Wilhelm-Allee, G. E39, 51373, Leverkusen, Germany., Schumacher CE; University of Cologne, Greinstrasse 4, 50939, Koeln, Germany., Sperlich J; TH Köln, Faculty of Applied Natural Sciences, Kaiser-Wilhelm-Allee, G. E39, 51373, Leverkusen, Germany., Neudörfl JM; University of Cologne, Greinstrasse 4, 50939, Koeln, Germany., Teusch N; TH Köln, Faculty of Applied Natural Sciences, Kaiser-Wilhelm-Allee, G. E39, 51373, Leverkusen, Germany., Hochgürtel M; TH Köln, Faculty of Applied Natural Sciences, Kaiser-Wilhelm-Allee, G. E39, 51373, Leverkusen, Germany., Schmalz HG; University of Cologne, Greinstrasse 4, 50939, Koeln, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Aug 11; Vol. 27 (45), pp. 11574-11579. Date of Electronic Publication: 2021 Jun 26.
DOI: 10.1002/chem.202101863
Abstrakt: Due to their pronounced bioactivity and limited availability from natural resources, metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, represent important target molecules for chemical synthesis. We have now developed a particularly short and efficient route towards these marine diterpenes exploiting an operationally convenient enantioselective cobalt-catalyzed hydrovinylation as the chirogenic step. Other noteworthy C-C bond forming transformations include diastereoselective Lewis acid-mediated cyclizations, a Suzuki coupling and a carbonyl ene reaction. Starting from 4-methyl-styrene the anti-tubercular agent (+)-erogorgiaene (>98 % ee) was prepared in only 7 steps with 46 % overall yield. In addition, the synthesis of the pseudopterosin A aglycone was achieved in 12 steps with 30 % overall yield and, surprisingly, was found to exhibit a similar anti-inflammatory activity (inhibition of LPS-induced NF-κB activation) as a natural mixture of pseudopterosins A-D or iso-pseudopterosin A, prepared by β-D-xylosylation of the synthetic aglycone.
(© 2021 The Authors. Published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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