Biomimetic syntheses of ineleganolide and sinulochmodin C from 5-episinuleptolide via sequences of transannular Michael reactions

Yi Li, Gerald Pattenden*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Citations (Scopus)

Abstract

Treatment of a solution of the macrocyclic norcembranoid 7 with lithium hexamethyldisilazide in THF at -78 °C to 0 °C, leads to the polycyclic norcembranoids ineleganolide 1 and sinulochmodin C (2) (65%), which are found in the corals Sinularia inelegans and Sinularia lochmodes, respectively. The conversions are believed to be biomimetic, and occur by successive transannular Michael reactions in 7. Under different temperature conditions the novel polycycle 30 is the main product, alongside small quantities of 1 and 2. The polycycle 30 is possibly produced from ineleganolide 1, following a reverse oxy-Michael reaction and two successive aldol reactions. The significance of the synthesis of ineleganolide 1, sinulochmodin C (2) and the structure 30 from 5-episinuleptolide 7, to the likely biosynthesis of the related norcembranoids scabrolide A (3), scabrolide B (4) and horiolide 31 found in Sinularia sp. is discussed.

Original languageEnglish
Pages (from-to)10045-10052
Number of pages8
JournalTetrahedron
Volume67
Issue number51
DOIs
Publication statusPublished - 23 Dec 2011
Externally publishedYes

Keywords

  • Biomimetic synthesis
  • Ineleganolide
  • Norcembranoid
  • Sinulochmodin C
  • Transannular cyclisation

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