Total synthesis of epoxyquinonoid natural products

Mitsuru Shoji

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

Asymmetric total synthesis of epoxyquinonoid natural products, such as epoxyquinols A, B, and C, epoxytwinol A, and EI-1941-1, -2, and -3, are described. In the first-generation synthesis of epoxyquinols, the HfCl 4-mediated diastereo-selective Diels-Alder reaction of furan with a chiral acrylate ester was developed. In the second-generation synthesis, a chromatography-free preparation of an iodolactone by using acryloyl chloride as the dienophile in the Diels-Alder reaction of furan, and the lipase-mediated kinetic resolution of a cyclohexenol derivative were developed. This second-generation synthesis is suitable for large-scale preparation. A biomimetic cascade reaction involving oxidation, 6π-elec-trocyclization, then Diels-Alder dimerization, is the key reaction in the formation of epoxyquinols A-C. Epoxytwinol A was synthesized by the cascade reaction composed of oxidation, 6π-electrocyclization, and formal [4 + 4] cycloaddition. A 2H-pyran, generated by oxidation/6π-electrocyclization, acts as a good diene, reacting with several dienophiles to afford polycyclic compounds in one step. The asymmetric total synthesis of EI-1941s was accomplished, starting from a chiral epoxy iodoquinone, a key intermediate in the total synthesis of epoxyquinols. They were diastereoselectively synthesized via an intramolecular carboxypalladation in a 6-endo cyclization mode, followed by β-hydride elimination, as the key steps.

Original languageEnglish
Pages (from-to)1672-1690
Number of pages19
JournalBulletin of the Chemical Society of Japan
Volume80
Issue number9
DOIs
Publication statusPublished - 2007
Externally publishedYes

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Biological Products
Oxidation
Polycyclic Compounds
Pyrans
Cycloaddition
Dimerization
Cyclization
Biomimetics
Chromatography
Lipase
Hydrides
Esters
Derivatives
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Total synthesis of epoxyquinonoid natural products. / Shoji, Mitsuru.

In: Bulletin of the Chemical Society of Japan, Vol. 80, No. 9, 2007, p. 1672-1690.

Research output: Contribution to journalArticle

Shoji, Mitsuru. / Total synthesis of epoxyquinonoid natural products. In: Bulletin of the Chemical Society of Japan. 2007 ; Vol. 80, No. 9. pp. 1672-1690.
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