Biomimetic Total Synthesis of HyperjaponesA-E and HyperjaponolsA andC

HyperjaponesA-E and hyperjaponolsA-C are complex natural products of mixed aromatic polyketide and terpene biosynthetic origin that have recently been isolated from Hypericum japonicum. We have synthesized hyperjaponesA-E using a biomimetic, oxidative hetero-Diels-Alder reaction to couple together d...

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Bibliographic Details
Published in:Angewandte Chemie 2016-08, Vol.128 (35), p.10524-10527
Main Authors: Lam, Hiu C, Spence, Justin T J, George, Jonathan H
Format: Article
Language:eng ; ger
Subjects:
Alkenes
Biomimetics
Carbon-carbon composites
Chemical bonds
Chemical synthesis
Chemistry
Couples
Epoxidation
Mimicry
Natural products
Olefins
Precursors
Synthesis (chemistry)
Terpenes
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Summary:HyperjaponesA-E and hyperjaponolsA-C are complex natural products of mixed aromatic polyketide and terpene biosynthetic origin that have recently been isolated from Hypericum japonicum. We have synthesized hyperjaponesA-E using a biomimetic, oxidative hetero-Diels-Alder reaction to couple together dearomatized acylphloroglucinol and cyclic terpene natural products. HyperjaponeA is proposed to be the biosynthetic precursor of hyperjaponolC through a sequence of: 1)epoxidation; 2)acid-catalyzed epoxide ring-opening; and 3)a concerted, asynchronous alkene cyclization and 1,2-alkyl shift of a tertiary carbocation. Chemical mimicry of this proposed biosynthetic sequence allowed a concise total synthesis of hyperjaponolC to be completed in which six carbon-carbon bonds, six stereocenters, and three rings were constructed in just four steps.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201606091