Divergent kinetic control of classical versus ozonolytic lactonization: Mechanism-based diastereoselection

Thomas R. Hoye, Troy D. Ryba

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

A strategy has been developed in which mechanistically distinct lactonization reactions are used to prepare diastereomeric δ-lactones relevant to the C1-C9 fragment of (+)-peloruside A. Depending upon which of two reaction types is used, the central (C5) hydroxyl group can be directed to differentiate the C1 versus C9 termini of pseudosymmetric substrates to provide diastereomeric lactones. Thus, the 5-hydroxy-1,9-diester substrate 1 (an azelaic ester) cyclizes under classical (acid- or base-catalyzed) lactonization conditions to give a predominance of one diastereomer, whereas the 5-hydroxy-1,10-diene congener 2 provides the opposite sense of diastereoselectivity when subjected to ozonolytic lactonization (O3, MeOH, NaOH, at -78 °C). Thus, this under-utilized oxidative transformation is mechanistically orthogonal to the classical reaction.

Original languageEnglish (US)
Pages (from-to)8256-8257
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number23
DOIs
StatePublished - Jun 15 2005

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