Efficient formal synthesis of (±)-Hyphodermin B
Author(s)
Henderson, LC
Loughlin, WA
Jenkins, ID
Healy, PC
Campitelli, MR
Year published
2006
Metadata
Show full item recordAbstract
An efficient formal synthesis of hyphodermin B 1, a metabolite of Hyphoderma radula, has been completed in 15% overall yield. The tricyclic carbon skeleton 3 was rapidly assembled from a novel vinyl enone via a Diels-Alder reaction, followed by dehydrogenation and anhydride formation. Selective reduction of anhydride 3 with LiAlH(t-BuO)3 gave hyphodermin B 1 in 99% yield. The structure of hyphodermin B 1 was confirmed by X-ray crystallographic analysis. The anhydride 3, bearing a ?-carbonyl group, displayed unexpected reactivity with the anhydride carbonyl closest to the ?-ketone being the most electrophilic site. This was ...
View more >An efficient formal synthesis of hyphodermin B 1, a metabolite of Hyphoderma radula, has been completed in 15% overall yield. The tricyclic carbon skeleton 3 was rapidly assembled from a novel vinyl enone via a Diels-Alder reaction, followed by dehydrogenation and anhydride formation. Selective reduction of anhydride 3 with LiAlH(t-BuO)3 gave hyphodermin B 1 in 99% yield. The structure of hyphodermin B 1 was confirmed by X-ray crystallographic analysis. The anhydride 3, bearing a ?-carbonyl group, displayed unexpected reactivity with the anhydride carbonyl closest to the ?-ketone being the most electrophilic site. This was confirmed by HF/6-31G* calculations. In the presence of base, 3 underwent a rearrangement to the novel lactone 16.
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View more >An efficient formal synthesis of hyphodermin B 1, a metabolite of Hyphoderma radula, has been completed in 15% overall yield. The tricyclic carbon skeleton 3 was rapidly assembled from a novel vinyl enone via a Diels-Alder reaction, followed by dehydrogenation and anhydride formation. Selective reduction of anhydride 3 with LiAlH(t-BuO)3 gave hyphodermin B 1 in 99% yield. The structure of hyphodermin B 1 was confirmed by X-ray crystallographic analysis. The anhydride 3, bearing a ?-carbonyl group, displayed unexpected reactivity with the anhydride carbonyl closest to the ?-ketone being the most electrophilic site. This was confirmed by HF/6-31G* calculations. In the presence of base, 3 underwent a rearrangement to the novel lactone 16.
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Journal Title
Journal of Organic Chemistry
Volume
71
Issue
6
Publisher URI
Copyright Statement
© 2006 American Chemical Society. Self-archiving of the author-manuscript version is not yet supported by this publisher. The contents of this journal can be freely accessed online via the ACS web page after publication. Use hypertext link above to access the ACS website.
Subject
Medicinal and biomolecular chemistry
Organic chemistry