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Synlett 2006(12): 1816-1828  
DOI: 10.1055/s-2006-947335
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Biomimetic Synthesis of trans,syn,trans-Fused Polycyclic Ethers

Jason C. Valentine, Frank E. McDonald*
Department of Chemistry, Emory University, Atlanta, GA 30322, USA
Fax: +1(404)7276586; e-Mail: fmcdona@emory.edu;
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Publication History

Received 24 February 2006
Publication Date:
24 July 2006 (online)

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Abstract

This account describes potentially biomimetic tandem regio- and stereoselective oxacyclizations of acyclic polyepoxide substrates to provide trans,syn,trans-fused polycyclic ether ­structures, as found in marine natural products exemplified by ­brevetoxins, ciguatoxins, and maitotoxin.

1 Introduction: Occurrence and Biological Activity of Fused Polycyclic Ether Natural Products

2 Biosynthetic Origins of Fused Polycyclic Ether Natural Products

3 Initial Studies Directed towards Tandem endo-Regioselective Cyclizations to Fused Polycyclic Ether Structures

4 Conversion of Terpene-Derived Polyepoxides to trans,syn,trans-Fused Polyoxepanes

5 Synthesis of trans,syn,trans-Polypyran from 1,4,7-Tri­epoxide

6 Substituent Effects on endo-Regioselective Poly­cyclizations

7 Future Directions for Exploration and Discovery

Key words

biomimetic synthesis - fused polycyclic ethers - poly­epoxides - regioselectivity - stereoselectivity

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3

The dinoflagellate implicated in red tide blooms in the Gulf of Mexico was first taxonomically classified as Gymnodinium breve, later as Ptychodiscus brevis and most recently as Karenia brevis. To avoid confusion, Karenia brevis will be used exclusively in this review.