Validating an endoperoxide as a key intermediate in the biosynthesis of elysiapyrones.
Compounds 1-3 isolated from Elysia diomedea are described. Compound 1 is an endoperoxide derivative of elysiapyrone A. The biomimetic-type transformation of compound 1 to elysiapyrone A catalyzed by neutral base transformed the endoperoxide to a vicinal diepoxide, thus suggesting the endoperoxide as a key intermediate in the biosynthesis of elysiapyrone A. A biogenetic pathway for their formation involving a cycloaddition of singlet oxygen to a polypropionate alkenyl open chain is proposed.
Instituto de Productos Naturales y Agrobiología del CSIC, La Laguna, Tenerife, Spain.
Ana R
AR
Díaz-Marrero
Mercedes
M
Cueto
Luis
L
D'Croz
José
J
Darias
D000818:Animals; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D008974:Mollusca / Q000737:chemistry; D010545:Peroxides / Q000737:chemistry*; D011753:Pyrones / Q000138:chemical synthesis* / Q000737:chemistry; D017382:Reactive Oxygen Species / Q000633:toxicity; D026082:Singlet Oxygen / Q000737:chemistry
D019086:Bridged Bicyclo Compounds, Heterocyclic; D010545:Peroxides; D011753:Pyrones; D017382:Reactive Oxygen Species; C509577:elysiapyrone A; C509578:elysiapyrone B; D026082:Singlet Oxygen