Diastereoselective total synthesis of both enantiomers of epolactaene

Yujiro Hayashi, Jun Kanayama, Junichiro Yamaguchi, Mitsuru Shoji

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

A stereocontrolled total synthesis of both the (+)- and (-)-epolactaene ((+)- and (-)-1) enantiomers from tetrahydropyran-2-ol is described. The following reactions in this synthesis are particularly noteworthy: (1) the stereoselective construction of the conjugated (E,E,E)-triene by a combination of kinetic deprotonation and thermodynamic equilibration, (2) the E-selective Knoevenagel condensation of β-ketonitrile 33 with a chiral 2-alkoxyaldehyde, (3) a diastereoselective epoxidation achieved using a bulky nucleophile (TrOOLi) and an appropriate protecting group, (4) the mild hydrolysis of an α-epoxy nitrile by silica gel on TLC facilitated by hydroxyl-mediated, intramolecular assistance.

Original languageEnglish
Pages (from-to)9443-9448
Number of pages6
JournalJournal of Organic Chemistry
Volume67
Issue number26
DOIs
Publication statusPublished - 2002 Dec 27
Externally publishedYes

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Enantiomers
Nitriles
Deprotonation
Nucleophiles
Epoxidation
Silica Gel
Hydroxyl Radical
Condensation
Hydrolysis
Thermodynamics
Kinetics
epolactaene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Diastereoselective total synthesis of both enantiomers of epolactaene. / Hayashi, Yujiro; Kanayama, Jun; Yamaguchi, Junichiro; Shoji, Mitsuru.

In: Journal of Organic Chemistry, Vol. 67, No. 26, 27.12.2002, p. 9443-9448.

Research output: Contribution to journalArticle

Hayashi, Y, Kanayama, J, Yamaguchi, J & Shoji, M 2002, 'Diastereoselective total synthesis of both enantiomers of epolactaene', Journal of Organic Chemistry, vol. 67, no. 26, pp. 9443-9448. https://doi.org/10.1021/jo025641m
Hayashi, Yujiro ; Kanayama, Jun ; Yamaguchi, Junichiro ; Shoji, Mitsuru. / Diastereoselective total synthesis of both enantiomers of epolactaene. In: Journal of Organic Chemistry. 2002 ; Vol. 67, No. 26. pp. 9443-9448.
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