Chemistry of epoxyquinols A, B, and C and epoxytwinol A

Mitsuru Shoji, Yujiro Hayashi

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The asymmetric total synthesis of epoxyquinols A, B, and C and epoxytwinol A, and computational analysis of the key biomimetic oxidative dimerization procedure are described. In the first-generation synthesis, a HfCl 4-mediated diastereoselective Diels-Alder reaction of furan with Corey's chiral auxiliary has been developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone using acryloyl chloride as the dienophile in the Diels-Alder reaction of furan and a lipase-mediated kinetic resolution of a cyclohexenol derivative have been developed. This second-generation synthesis is suitable for large-scale synthesis. A biomimetic cascade reaction involving oxidation, 6π-electrocyclization, and then Diels-Alder dimerization is the key reaction in the formation of the complex heptacyclic structure of epoxyquinols A, B, and C. Epoxytwinol A is synthesized by the cascade reaction involving oxidation, 6π-electrocyclization, and formal [4+4] cycloaddition reactions. A 2H-pyran, generated by oxidation/6π-electrocyclization, acts as a good diene, reacting with several dienophiles to afford polycyclic compounds in one step.

Original languageEnglish
Pages (from-to)3783-3800
Number of pages18
JournalEuropean Journal of Organic Chemistry
Issue number23
DOIs
Publication statusPublished - 2007
Externally publishedYes

Fingerprint

chemistry
synthesis
Diels-Alder reactions
Dimerization
furans
biomimetics
Biomimetics
dimerization
Oxidation
oxidation
cascades
Polycyclic Compounds
Pyrans
Cycloaddition
cycloaddition
dienes
chromatography
Chromatography
Lipase
chlorides

Keywords

  • Density functional calculations
  • Diels-Alder reactions
  • Electrocyclic reactions
  • Epoxyquinols A, B, C
  • Epoxytwinol A
  • Total synthesis

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Chemistry of epoxyquinols A, B, and C and epoxytwinol A. / Shoji, Mitsuru; Hayashi, Yujiro.

In: European Journal of Organic Chemistry, No. 23, 2007, p. 3783-3800.

Research output: Contribution to journalArticle

Shoji, Mitsuru ; Hayashi, Yujiro. / Chemistry of epoxyquinols A, B, and C and epoxytwinol A. In: European Journal of Organic Chemistry. 2007 ; No. 23. pp. 3783-3800.
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