A strategy towards the synthesis of plumarellide based on biosynthesis speculation, featuring a transannular 4+2 type cyclisation from a cembranoid furanoxonium ion intermediate

Yi Li, Matthew J. Palframan, Gerald Pattenden*, Johan M. Winne

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

18 Citations (Scopus)

Abstract

In studies towards a biomimetic synthesis of plumarellide 1, acid-catalysed rearrangement of the furanobutenolide-based acetonide 10b led to the ring system 15b in plumarellide together with the cycloheptene-based ring system 11 found in rameswaralide 4, in a combined yield of 60%. RCM of the ω-dienes 30a and 30b led to the macrocycles 38a and 38b, respectively with the Z-configuration. Treatment of the vinyl bromide/vinyl stannanes 32a and 47 under Stille conditions failed to give the macrocycles 31a and 48, respectively. Reactions of the macrocycles 38a and 38b with TFA containing water produced the 5,6,7-tricyclic compounds 56a and 56b, respectively in >90% yield, instead of the plumarellide-based ring system 52. A summary and perspective on possible pathways from the C-13 acetoxy furanocembranoid 66 and from the C13–C14 unsaturated enol ether/cyclic hemiketal 9/59 to plumarellide 1 in vivo is given.

Original languageEnglish
Pages (from-to)7229-7240
Number of pages12
JournalTetrahedron
Volume70
Issue number40
DOIs
Publication statusPublished - 2014
Externally publishedYes

Keywords

  • Biomimetic
  • Furanoxonium ion
  • Macrocyclisation
  • Plumarellide
  • Rameswaralide

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