Biomimetic Syntheses of Amorfrutin C and C‐5 Substituted Amorfrutin Analogues. Issue 8 (11th February 2021)

• Record Type: Journal Article
• Authors: Patel, Calum; Mies, Thomas; White, Andrew J. P.; Parsons, Philip J.; Barrett, Anthony G. M.
• Is Part Of: European journal of organic chemistry. Issue 8(2021)
• Page Start: 1258
• Page End: 1265
• Publication Date: 2021-02-11
• Subjects: Aromatization -- Biomimetic synthesis -- Cyclization -- Ketenes -- Natural products; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.202001487
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: Amorfrutin C, a C ‐5 prenyl amorfrutin, its allyl analog and an amorfrutin C ‐5 aldehyde have been synthesized using a biomimetic strategy from non‐aromatic precursors. In this approach, a dioxinone derived β, δ‐ diketo ester underwent a decarboxylative Pd(0) catalyzed prenyl migration to give a β, δ‐ diketo dioxinone, which readily aromatized giving the amorfrutin core. The introduction of prenyl and allyl moieties at the C ‐5 position of the scaffold was accomplished using a Claisen rearrangement. Alternatively, iodination, lithium‐iodine exchange and trapping with DMF gave the amorfrutin aldehyde and an amorfrutin alcohol when excess n ‐BuLi was used. Abstract : Amorfrutin C, a C ‐5 prenyl substituted amorfrutin, its allyl analog and an amorfrutin C‐5 aldehyde derivate have been synthesized from a common amorfrutin intermediate, which was prepared via a biomimetic β, δ ‐diketo‐dioxinone aromatization reaction.