Total Synthesis of (±)-Hyphodermins A and D
Author(s)
Loughlin, Wendy A
Jenkins, Ian D
Henderson, Luke C
Campitelli, Marc R
Healy, Peter C
Year published
2008
Metadata
Show full item recordAbstract
An efficient formal synthesis of (()-hyphodermins A and D, metabolites of Hyphoderma radula, has been completed in 12 and 11 steps, respectively. The tricyclic carbon skeleton of enone 6 was rapidly assembled from diester 11 via an R brominationn-elimination sequence followed by anhydride formation. Regioselective reduction of the lactone group of enone 6 with LiAlH(t-BuO)3 gave lactol 15. Lactol 15 was converted in two steps to (()-hyphodermin D, without the need for complex protection-deprotection strategies. Lactol 15 was converted in three steps to (()-hyphodermin A, via the key step of epoxidation of an enone in the ...
View more >An efficient formal synthesis of (()-hyphodermins A and D, metabolites of Hyphoderma radula, has been completed in 12 and 11 steps, respectively. The tricyclic carbon skeleton of enone 6 was rapidly assembled from diester 11 via an R brominationn-elimination sequence followed by anhydride formation. Regioselective reduction of the lactone group of enone 6 with LiAlH(t-BuO)3 gave lactol 15. Lactol 15 was converted in two steps to (()-hyphodermin D, without the need for complex protection-deprotection strategies. Lactol 15 was converted in three steps to (()-hyphodermin A, via the key step of epoxidation of an enone in the presence of a THP lactol. A combination of NMR and ab initio studies suggests that the structures of hyphodermin C and D should be interchanged.
View less >
View more >An efficient formal synthesis of (()-hyphodermins A and D, metabolites of Hyphoderma radula, has been completed in 12 and 11 steps, respectively. The tricyclic carbon skeleton of enone 6 was rapidly assembled from diester 11 via an R brominationn-elimination sequence followed by anhydride formation. Regioselective reduction of the lactone group of enone 6 with LiAlH(t-BuO)3 gave lactol 15. Lactol 15 was converted in two steps to (()-hyphodermin D, without the need for complex protection-deprotection strategies. Lactol 15 was converted in three steps to (()-hyphodermin A, via the key step of epoxidation of an enone in the presence of a THP lactol. A combination of NMR and ab initio studies suggests that the structures of hyphodermin C and D should be interchanged.
View less >
Journal Title
Journal of Organic Chemistry
Volume
73
Issue
9
Publisher URI
Copyright Statement
© 2008 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