CC BY-ND-NC 4.0 · Synthesis 2019; 51(01): 285-295
DOI: 10.1055/s-0037-1610387
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Synthesis of the C1–C12 Fragment of Calyculin C

a   Aalto University School of Chemical Engineering, Department of Chemistry and Materials Science, Kemistintie 1, P.O. Box 16100, 02150 Espoo, Finland   Email: ari.koskinen@aalto.fi
b   Latvian Institute of Organic Synthesis, Aizkraukles 21, LV-1006, Riga, Latvia
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a   Aalto University School of Chemical Engineering, Department of Chemistry and Materials Science, Kemistintie 1, P.O. Box 16100, 02150 Espoo, Finland   Email: ari.koskinen@aalto.fi
› Author Affiliations
This work was supported by the Academy of Finland (project number 266369) and (to O.V.K.) the FP7 InnovaBalt project (contract Nr.316149). The authors would like to acknowledge the networking contribution by COST Action CM1407 “Challenging organic syntheses inspired by nature – from natural products chemistry to drug discovery”.
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Publication History

Received: 26 September 2018

Accepted after revision: 26 October 2018

Publication Date:
22 November 2018 (online)


Dedicated to the memory of Professor István E. Markó.

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Calyculins are a class of highly cytotoxic metabolites originally isolated from the marine sponge Discodermia calyx. To date, a total of twelve different calyculins (A–J) and calyculinamides (A, B and F) have been described, the most abundant (in D. calyx) being calyculins A and C. Herein, we demonstrate a concise route to access the C1–C12 tetraene fragment of calyculin C using transition-metal-catalyzed coupling reactions (Suzuki–Miyaura, Stille, Negishi and Heck) for the key connections. The synthesis starts from propionaldehyde and proceeds in 10 steps with 7.5% overall yield. We also describe an efficient route for the preparation of (Z)-3-iodobut-2-enenitrile in four steps and 68% yield.

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