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. 2021 Feb 8;60(6):2939-2942.
doi: 10.1002/anie.202011298. Epub 2020 Dec 10.

Total Synthesis of the Diterpene Waihoensene

Lisa-Catherine Rosenbaum  1 , Maximilian Häfner  1 , Tanja Gaich  1
Affiliations

Total Synthesis of the Diterpene Waihoensene

Lisa-Catherine Rosenbaum et al. Angew Chem Int Ed Engl. .

Abstract

A racemic and scalable enantioselective total synthesis of (+)-waihoensene was accomplished. (+)-Waihoensene belongs to the diterpene natural product family, and it features an angular triquinane substructure motif. Its tetracyclic [6.5.5.5]backbone is all-cis-fused, containing six contiguous stereocenters, four of which are quaternary. These structural features were efficiently installed by means of a diastereoselective radical cyclization, followed by an intramolecular Pauson-Khand reaction, a diastereoselective α-alkylation, and a diastereoselective 1,4-addition reaction. Enantioselectivity was introduced at an early stage, by an asymmetric palladium catalyzed decarboxylative allylation reaction on gram scale.

Keywords: Pauson-Khand reaction; natural products; radicals; terpenes; total synthesis.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Comparison of the linear and angular triquinane structure element.
Figure 2
Figure 2
Synthetic strategies of previous syntheses.
Figure 3
Figure 3
Retrosynthetic analysis this work's synthesis.
Scheme 1
Scheme 1
Synthesis of the Pauson–Khand precursor 12.
Scheme 2
Scheme 2
Pauson–Khand reaction of 12 and endgame to waihoensene (1).
Scheme 3
Scheme 3
Enantioselective approach to (+)‐waihoensene (1) by an asymmetric allylation reaction.
See this image and copyright information in PMC

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