Synthesis of (±)-Nephromopsinic, (−)-Phaseolinic, and (−)-Dihydropertusaric Acids

✍ Scribed by Andrea Brecht-Forster; Juliette Fitremann; Philippe Renaud

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: German
• Weight: 190 KB
• Volume: 85
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/1522-2675(200211)85:11<3965::aid-hlca3965>3.0.co;2-2

✦ Synopsis

Dedicated to Professor Dieter Seebach for his formidable and communicative enthusiasm for chemistry

The formal syntheses of (AE)-nephromopsinic acid, (À)-phaseolinic acid, and the first total synthesis of (À)dihydropertusaric acid from (AE)-and (À)-7-oxabicyclo[2.2.1]hept-5-en-2-one are described. These syntheses take advantage of a previously reported radical rearrangement (1,2-acyl migration). A remarkable iodidemediated cleavage of a bicyclic system, followed by the introduction of the g-chains via a mixed Kolbe electrolysis, are the key steps of these syntheses. This approach is general and could be applied for the preparation of all kinds of paraconic acids with excellent control of the stereochemistry.