Synthesis of the C1–C12 Fragment of Calyculin C

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.

Key words

calyculins - natural products - transition-metal-catalyzed cross-coupling - Suzuki–Miyaura - Stille - Negishi and Heck coupling - syntheses of di- and polyenes

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