A reductive coupling strategy towards ripostatin A
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Jamison_A reductive coupling.pdf
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Author(s)
Schleicher, Kristin D.
Jamison, Timothy F.
Date Issued
July 2013
Journal
Beilstein Journal of Organic Chemistry
Publisher
Beilstein-Institut
Citation
Schleicher, Kristin D, and Timothy F Jamison. “A reductive coupling strategy towards ripostatin A.” Beilstein Journal of Organic Chemistry 9 (July 31, 2013): 1533-1550.
Version
Author's final manuscript
Abstract
Synthetic studies on the antibiotic natural product ripostatin A have been carried out with the aim to construct the C9−C10 bond by a nickel(0)-catalyzed coupling reaction of an enyne and an epoxide, followed by rearrangement of the resulting dienylcyclopropane intermediate to afford the skipped 1,4,7-triene. A cyclopropyl enyne fragment corresponding to C1−C9 has been synthesized in high yield and demonstrated to be a competent substrate for the nickel(0)-catalyzed coupling with a model epoxide. Several synthetic approaches toward the C10−C26 epoxide have been pursued. The C13 stereocenter can be set by allylation and reductive decyanation of a cyanohydrin acetonide. A mild, fluoride-promoted decarboxylation enables construction of the C15−C16 bond by an aldol reaction. The product of this transformation is of the correct oxidation state and potentially three steps removed from the targeted epoxide fragment.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.3762/bjoc.9.175
