Total Synthesis of Shearinines D and G: A Convergent Approach to Indole Diterpenoids.

Autor: Hauser N; Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 3, HCI H335, 8093, Zürich, Switzerland., Imhof MA; Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 3, HCI H335, 8093, Zürich, Switzerland., Eichenberger SS; Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 3, HCI H335, 8093, Zürich, Switzerland., Kündig T; Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 3, HCI H335, 8093, Zürich, Switzerland., Carreira EM; Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir Prelog Weg 3, HCI H335, 8093, Zürich, Switzerland.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Jan 17; Vol. 61 (3), pp. e202112838. Date of Electronic Publication: 2021 Dec 09.
DOI: 10.1002/anie.202112838
Abstrakt: The first total syntheses of the indole diterpenoids (+)-shearinine G and D are disclosed. The successful routes rely on late-stage coupling of two complex fragments. Formation of the challenging trans-hydrindane motif was accomplished by diastereoselective, intramolecular cyclopropanation. A one-pot sequence consisting of Sharpless dihydroxylation/Achmatowicz reaction was developed to install the dioxabicyclo[3.2.1]octane motif. The indenone subunit was accessed by Prins cyclization. Tuning the electronic nature of the substituents on the parent arylcarboxaldehyde allowed access to divergent products that were further transformed into shearinines G and D. Riley-type oxidation of a bicyclic enone yielded a surprising stereochemical outcome.
(© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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