A Formal Total Synthesis of the Sesterterpenoid (±)-Dysidiolide and Approaches to the Syntheses of (±)-6-Epi-, (±)-15-Epi-, and (±)-6,15-Bisepidysidiolide

Abstract

A formal total synthesis of the sesterterpenoid (+/-)-dysidiolide (1), a structurally novel sponge metabolite that inhibits the cdc25A protein phosphatase, and approaches to the syntheses of (+/-)-15-epi- (34), (+/-)-6-epi- (36), and (+/-)-6, 15-bisepidysidiolide (39) are described.

Unusual cyclic terpenoids with terminal pendant prenyl moieties: from occurrence to synthesis

“…118,119 Latter on, a lot of papers have been published either on the total or formal syntheses of disidiolide. [120][121][122][123][124][125][126][127][128][129][130][131][132] The applied strategic approaches were different and their discussion will be provided in a separate section of the present review.…”

Marine natural products

“…344,345 Four additional syntheses of the cytotoxic agent dysidiolide 468, which was isolated from Dysidea etheria, 346 have been reported. [347][348][349][350] A specimen of Theonella swinhoei from the Philippines contained 7α-hydroxytheonellasterol 469 as a mildly cytotoxic constituent of the sterol fraction. 351 Polymastia sobustia from the South China Sea contained 3β-hydroxystigmast-5-en-7-one 470.…”

Synthetic approaches toward sesterterpenoids

“…Finally, a six step protocol led to aldehyde 93, the common intermediate from the Corey and Danishefsky syntheses, that was converted to racemic dysidiolide (88) as previously described (Scheme 11). Other racemic formal syntheses by the groups of Piers 70 and Maier 71 were published in the same year, also opting to close the decalin system utilizing an intramolecular aldol condensation.…”