Epoxycaulerpenynes: Reactivity, and Diastereoselective and Highly Regioselective Synthesis by Dimethyldioxirane Oxidation of Caulerpenyne

✍ Scribed by Antonio Guerriero; Michele D'Ambrosio

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 258 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/(sici)1099-0690(199908)1999:8<1985::aid-ejoc1985>3.0.co;2-o

✦ Synopsis

Caulerpenyne (1), the abundant sesquiterpene of the green mixture 8. The epoxides underwent rearrangement under acidic conditions; the 6,7-epoxides were easily converted into seaweed Caulerpa taxifolia, has been epoxidized with dimethyldioxirane. The reaction proceeds with significant allylic alcohols, whereas the 10,11 isomers required more drastic acidic conditions and gave complex mixtures regioselectivity and moderate diastereoselectivity, the addition of oxygen occurring preferentially at the C( 6)=C( 7) containing two diastereoisomeric 1,4-dioxanes and an enynone. The high reactivity of 6,7-epoxycaulerpenynes double bond thereby giving (6S,7S)-and (6R,7R)epoxycaulerpenynes 10 and 12 in an approximately 2:1 suggests their involvement in the biogenetic pathways of the alga. molar ratio besides a small amount of 10,11epoxycaulerpenyne as an equimolecular diastereomeric