Cyclobutenone-based syntheses of polyquinanes and bicyclo[6.3.0]undecanes by tandem anionic oxy-cope reactions. Total synthesis of (±)-precapnelladiene

James M. MacDougall, Vincent J. Santora, Sharad K. Verma, Philip Turnbull, Cameron R. Hernandez, Harold W. Moore

Research output: Contribution to journalArticlepeer-review

Abstract

The addition of ethenyllithium derivatives to the carbonyl of dialkyl squarate-derived bicycloheptenones, e.g., la and 6a, initiates a low-temperature anion-accelerated oxy-Cope rearrangement to provide polyquinanes by a transannular aldol reaction of the intermediate bicyclo[6.3.0]-undecadienone 4. Additional functionality is introduced by alkylation of the enolate 3 resulting from the oxy-Cope rearrangement. Phosphorylation or triflation of enolate 3 provides an entry into the bicyclo[6.3.0]undecane ring system. An application of this new methodology is demonstrated by the total synthesis of the sesquiterpene natural product (±)-precapnelladiene from diisopropyl squarate (10 steps, 12%).

Original languageEnglish (US)
Pages (from-to)6905-6913
Number of pages9
JournalJournal of Organic Chemistry
Volume63
Issue number20
DOIs
StatePublished - Oct 2 1998
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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