Enantioselective total syntheses of (+)-decursin and related natural compounds using catalytic asymmetric epoxidation of an enone

Tetsuhiro Nemoto, Takashi Ohshima, Masakatsu Shibasaki

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

The enantioselective total syntheses of (+)-decursin (1) and related natural dihydropyranocoumarins (-)-prantschimgin (3), (+)-decursinol (4), and (+)-marmesin (5) were achieved for the first time using catalytic asymmetric epoxidation of an enone as the key step. Catalytic asymmetric epoxidation of the enone was effectively promoted by the novel multifunctional asymmetric catalyst generated from La(O-i-Pr)3, BINOL, and Ph3As=O in a 1:1:1 ratio to afford epoxide in 94% yield and 96% ee, which was recrystallized to give optically pure epoxide. After conversion to the common key intermediate (-)-peucedanol (7), all natural dihydropyranocoumarins were synthesized through palladium-catalyzed intramolecular C-O coupling reactions. A possible reaction mechanism of the catalytic asymmetric epoxidation of enones is also described based on X-ray analysis, laser desorption/ionization time-of-flight mass spectrometry, kinetic studies, and asymmetric amplification studies.

Original languageEnglish
Pages (from-to)6889-6897
Number of pages9
JournalTetrahedron
Volume59
Issue number35
DOIs
Publication statusPublished - Aug 25 2003
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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