Synthesis of (-)-morphine: Application of sequential claisen/claisen rearrangement of an allylic vicinal diol

Masato Ichiki, Hiroki Tanimoto, Shohei Miwa, Ryosuke Saito, Takaaki Sato, Noritaka Chida

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

A detailed exploration of the synthesis of (-)-morphine based on sequential [3,3]-sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel-Crafts-type cyclization. The (-)-morphine double bond was introduced at a late stage in our first-generation synthesis, but was formed at an earlier stage in the second-generation synthesis, resulting in a more efficient route to the end product.

Original languageEnglish
Pages (from-to)264-269
Number of pages6
JournalChemistry - A European Journal
Volume19
Issue number1
DOIs
Publication statusPublished - 2013 Jan 2

Keywords

  • allylic compounds
  • chirality
  • morphine
  • sigmatropic rearrangement
  • total synthesis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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