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. 2014 Jan 22;136(3):870-3.
doi: 10.1021/ja411539w. Epub 2013 Dec 9.

Total synthesis of (-)-calyciphylline N

Artem Shvartsbart  1 , Amos B Smith 3rd
Affiliations

Total synthesis of (-)-calyciphylline N

Artem Shvartsbart et al. J Am Chem Soc. .

Abstract

The total synthesis of the architecturally complex Daphniphyllum alkaloid (-)-calyciphylline N has been achieved. Highlights of the synthesis include a Et2AlCl-promoted, highly stereoselective, susbtrate-controlled intramolecular Diels-Alder reaction, a transannular enolate alkylation, an effective Stille carbonylation/Nazarov cyclization sequence, and a high-risk diastereoselective hydrogenation of a fully substituted conjugated diene ester.

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Figures

Figure 1
Figure 1
(−)-Calyciphylline N and related congeners.
Figure 2
Figure 2
Retrosynthetic Analysis.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Scheme 3
Scheme 3
Scheme 4
Scheme 4
Scheme 5
Scheme 5
Scheme 6
Scheme 6
Scheme 7
Scheme 7
See this image and copyright information in PMC

References

    1. Kobayashi J, Kubota T. Nat Prod Rep. 2009;26:936. - PubMed

    1. For recent synthetic studies, see: Coldham I, Watson L, Adams H, Martin NG. J Org Chem. 2011;76:2360.Darses B, Michaelides IN, Sladojevich F, Ward JW, Rzepa PR, Dixon DJ. Org Lett. 2012;14:1684.

    1. For an elegant total synthesis of the closely related congener, (+)-daphmanidin E (Figure 1), see: Weiss ME, Carreira EM. Angew Chem Int Ed. 2011;50:11501.

    1. For a very recent total synthesis of the Daphniphyllum alkaloid, daphenylline (Figure 1), see: Lu ZY, Li Y, Deng J, Li A. Nat Chem. 2013;5:679.

    1. Yahata H, Kubota T, Kobayashi J. J Nat Prod. 2008;72:148. - PubMed

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