Development of a Unified Enantioselective, Convergent Synthetic Approach Toward the Furanobutenolide-Derived Polycyclic Norcembranoid Diterpenes: Asymmetric Formation of the Polycyclic Norditerpenoid Carbocyclic Core by Tandem Annulation Cascade

The Journal of Organic Chemistry
Robert A CraigBrian M Stoltz

Abstract

An enantioselective and diastereoselective approach toward the synthesis of the tetracyclic scaffold of the furanobutenolide-derived polycyclic norditerpenoids is described. Focusing on synthetic efforts toward ineleganolide, the synthetic approach utilizes a palladium-catalyzed enantioselective allylic alkylation for the construction of the requisite chiral tertiary ether. A diastereoselective cyclopropanation-Cope rearrangement cascade enabled the convergent assembly of the ineleganolide [6,7,5,5]-tetracyclic scaffold. Investigation of substrates for this critical tandem annulation process is discussed along with synthetic manipulations of the [6,7,5,5]-tetracyclic scaffold and the attempted interconversion of the [6,7,5,5]-tetracyclic scaffold of ineleganolide to the isomeric [7,6,5,5]-core of scabrolide A and its naturally occurring isomers. Computational evaluation of ground-state energies of late-stage synthetic intermediates was used to guide synthetic development and aid in the investigation of the conformational rigidity of these highly constrained and compact polycyclic structures.

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Citations

Nov 6, 2018·Chemical Society Reviews·Zengsheng YinPauline Chiu
Sep 22, 2020·ChemistryOpen·Lukas Junk, Uli Kazmaier
Jun 11, 2020·Chemistry, an Asian Journal·Karuppu SelvarajK C Kumara Swamy
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Jun 4, 2021·Organic Letters·Sanghyeon LeeHee-Yoon Lee
Jun 7, 2018·Organic Letters·Martín J RiveiraAgustina La-Venia
Jun 19, 2018·The Journal of Organic Chemistry·Andrei G KutateladzeTina Holt

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