Total synthesis of solandelactones A, B, E, and F exploiting a tandem petasis-claisen lactonization strategy

James D. White, Christopher Lincoln, Jongtae Yang, William H.C. Martin, David B. Chan

Research output: Contribution to journalArticle

40 Scopus citations

Abstract

(Chemical Equation Presented) Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyama-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (75) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C22 oxylipins that parallels a hypothesis put forward previously to explain the origin of C20 cyclopropane-containing algal products.

Original languageEnglish (US)
Pages (from-to)4139-4150
Number of pages12
JournalJournal of Organic Chemistry
Volume73
Issue number11
DOIs
StatePublished - Jun 6 2008

ASJC Scopus subject areas

  • Organic Chemistry

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