Synthetic studies towards pentacyclic quassinoids: Total synthesis of unnatural (-)-14-epi-samaderine e and natural (-)-samaderine y from (S)-(+)-carvone

Tony K.M. Shing, Ying Yeung Yeung

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

First total syntheses of unnatural (-)-14-epi-samaderine E (5) and natural (-)-samaderine Y (2) were accomplished from (5)-(+)-carvone (6) in 18 and 21 steps, respectively. The syntheses are short, efficient (with an average yield of 80% plus for each transformation), enantiospecific, and produce nine new chiral centers. The crucial points of the syntheses included a regioselective allylic oxidation on ring C, regio- and stereoselective reduction of ketone, a stereocontrolled epoxidation, an epoxymethano-bridge formation, a chemoselective Grignard reaction, an intramolecular Diels-Alder reaction, an intramolecular aldol addition, and a newly developed manganese(III)-catalyzed allylic oxidation on ring A.

Original languageEnglish
Pages (from-to)8367-8377
Number of pages11
JournalChemistry - A European Journal
Volume12
Issue number32
DOIs
Publication statusPublished - 2006 Nov 6

Keywords

  • Allylic oxidation
  • Antitumor agents
  • Cycloaddition
  • Quassinoids
  • Total synthesis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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