Synthesis of three marine natural sesterterpenolides from methyl isoanticopalate. First enantioselective synthesis of luffolide.
[Reaction: see text]. The synthesis of three marine sponge metabolites, luffolide (4), 5, and 6, are described for the first time, establishing the absolute configuration of these compounds. The key intermediate, aldehyde 17, was obtained from methyl isoanticopalate, 11. The addition of 3-furyllithium to 17 and subsequent photochemical oxidation give the gamma-hydroxybutenolide 5 and its epimer at C-16. Sesterterpenolide 6 is obtained by dehydration of 5. From the key aldehyde 17, luffolide (4) was obtained in six steps.
Basabe
P
P
Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad de Salamanca, Plaza de los Caídos 1-5, 37008 Salamanca, Spain. pbb@usal.es
Delgado
S
S
Marcos
I S
IS
Diez
D
D
Diego
A
A
De Román
M
M
Urones
J G
JG
D000447:Aldehydes / Q000737:chemistry; D000818:Animals; D004224:Diterpenes / Q000737:chemistry; D008968:Molecular Conformation; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010777:Photochemistry; D011161:Porifera / Q000737:chemistry*; D012717:Sesquiterpenes / Q000138:chemical synthesis*; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis* / Q000737:chemistry
D000447:Aldehydes; D004224:Diterpenes; D012717:Sesquiterpenes; D013729:Terpenes; C059349:luffolide; C475224:copalol