An enantioselective formal synthesis of 4-demethoxydaunomycin using the catalytic asymmetric ring opening reaction of meso-epoxide with p-anisidine

Akihiro Sekine, Takashi Ohshima, Masakatsu Shibasaki

Research output: Contribution to journalArticle

95 Citations (Scopus)

Abstract

A catalytic asymmetric formal synthesis of 4-demethoxydaunomycin (3) was achieved using a catalytic asymmetric ring opening reaction of meso-epoxide 9 as a key step. The epoxide opening reaction was promoted by 10 mol% of Pr-(R)-BINOL-Ph3P=O complex to give the β-amino alcohol 11 in 80% yield with 65% enantiomeric excess (ee). Single recrystallization enhanced the enantiomeric purity of the β-amino alcohol 11 to 95% ee. The β-amino alcohol 11 was then converted to the known key intermediate 6 through several steps, including a methylation, Hofmann elimination, an oxymercuration, and addition of an ethynyl group in a highly diastereoselective manner.

Original languageEnglish
Pages (from-to)75-82
Number of pages8
JournalTetrahedron
Volume58
Issue number1
DOIs
Publication statusPublished - Jan 1 2002
Externally publishedYes

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Amino Alcohols
Epoxy Compounds
Methylation
4-anisidine

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

An enantioselective formal synthesis of 4-demethoxydaunomycin using the catalytic asymmetric ring opening reaction of meso-epoxide with p-anisidine. / Sekine, Akihiro; Ohshima, Takashi; Shibasaki, Masakatsu.

In: Tetrahedron, Vol. 58, No. 1, 01.01.2002, p. 75-82.

Research output: Contribution to journalArticle

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