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Merck

Study of the total synthesis of (-)-exiguolide.

The Journal of organic chemistry (2012-08-02)
Cyril Cook, Frédéric Liron, Xavier Guinchard, Emmanuel Roulland
摘要

In this article, we disclose the various routes and strategies we had to explore before finally achieving the total synthesis of (-)-exiguolide ((-)-1). Two first types of approaches were set, both relying on the Trost's domino ene-yne coupling/oxa-Michael reaction that we choose for its ability to control the geometry of the methylacrylate-bearing tetrahydropyrane ring B. In our first approach, we expected to assemble the two main fragments (C14-C21 and C1-C13) by creating the C13-C14 bond through a palladium(0)-catalyzed cross-coupling, but this step failed, unfortunately. In the second approach, which was more linear, we created the C16-C17 bond through condensation of a lithium acetylide on a Weinreb amide, and we assembled the C1-C5 and C6-C21 subunits through Trost's domino ene-yne coupling/oxa-Michael reaction. These two approaches served us to design an ameliorated third strategy, which finally led to the total synthesis of (-)-exiguolide.

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Sigma-Aldrich
丙烯酸甲酯, 99%, contains ≤100 ppm monomethyl ether hydroquinone as inhibitor
Supelco
丙烯酸甲酯, analytical standard