Formal total synthesis of (+)-diepoxin sigma

P Wipf; J K Jung

doi:10.1021/jo000684t

Formal total synthesis of (+)-diepoxin sigma

J Org Chem. 2000 Oct 6;65(20):6319-37. doi: 10.1021/jo000684t.

Authors

P Wipf¹, J K Jung

Affiliation

¹ Department of Chemistry, University of Pittsburgh, Pennsylvania 15260, USA. pwipf+@pitt.edu

PMID: 11052073
DOI: 10.1021/jo000684t

Abstract

The highly oxygenated antifungal anticancer natural product (+/-)-diepoxin sigma was prepared in 10 steps and in 15% overall yield from O-methylnaphthazarin. Highlights of the synthetic work include an Ullmann coupling and a possibly biomimetic oxidative spirocyclization for the introduction of the naphthalene ketal as well as the use of a retro-Diels-Alder reaction to unmask the reactive enone moiety in the naphthoquinone bisepoxide ring system. A novel highly bulky chiral binaphthol ligand was developed for a boron-mediated Diels-Alder reaction that constitutes a formal asymmetric total synthesis of (+)-diepoxin sigma.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Africa
Crystallography, X-Ray
Epoxy Compounds / chemical synthesis*
Plants, Medicinal / chemistry*
Spiro Compounds / chemical synthesis*

Substances

Epoxy Compounds
Spiro Compounds
diepoxin sigma