Gold(I)-mediated cycloisomerization/cycloaddition enables bioinspired syntheses of neonectrolides B-E and analogues
Purgett, Thomas J.
Dyer, Matthew W.
Porco, John A.
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Citation (published version)Thomas J Purgett, Matthew W Dyer, Bryce Bickel, James McNeely, John A Porco. 2019. "Gold(I)-Mediated Cycloisomerization/Cycloaddition Enables Bioinspired Syntheses of Neonectrolides B-E and Analogues.." J Am Chem Soc, Volume 141, Issue 38, pp. 15135 - 15144. https://doi.org/10.1021/jacs.9b06355
Development of a synthetic route to the oxaphenalenone (OP) natural products neonectrolides B-E is described. The synthesis relies on gold-catalyzed 6-endo-dig hydroarylation of an unusual enynol substrate as well as a one-pot Rieche formylation/cyclization/deprotection sequence to efficiently construct the tricyclic oxaphenalenone framework in the form of a masked ortho-quinone methide (o-QM). A tandem cycloisomerization/[4 + 2] cycloaddition strategy was employed to quickly construct molecules resembling the neonectrolides. The tricyclic OP natural product SF226 could be converted to corymbiferan lactone E and a related masked o-QM. Our study culminates with the application of the tandem reaction sequence to syntheses of neonectrolides B-E as well as previously unreported exo-diastereomers.
The publisher's final edited version of this article is available at J Am Chem Soc. doi: 10.1021/jacs.9b06355