New terpenoid metabolites from the skin extracts, an egg mass, and dietary sponges of the Northeastern Pacific dorid nudibranch Cadlinaluteomarginata

Abstract

Chemical investigations of Cadlinaluteomarginata skin extracts, egg masses, and dietary sponges have led to the identification of the novel terpenoids cadlinaldehyde (30), spongian 32, seco-spongian 35, 20-acetoxy-12-marginatone (38), and lutenolide (39) from the nudibranch skin extracts, the new drimane sesquiterpenoid 1α,2α-diacetoxyalbicanyl acetate (40) from the nudibranch's egg mass, and the new sesquiterpenoids O-methyl-9-oxofurodysininlactone (47), 2-oxomicro-cionin-2-lactone (48), and O-methyl-2-oxomicrocionin-2-lactone (49), from the dietary sponge Pleraplysilla sp. The known terpenoids furodysinin (1), furodysin (16), marginatafuran (21), and 9,11-dihydrogracillin A (37), which have been frequently isolated from C. luteomarginata skin extracts, were found for the first time in extracts of the dietary sponges Pleraplysilla sp. and Aplysilla sp. One of the new terpenoids, cadlinaldehyde (30), has an unprecedented degraded sesterterpenoid skeleton. Keywords: nudibranch, sponge, terpenoids, structure elucidation.

The chemistry and chemical ecology of nudibranchs

“…To date, 38 terpenoid metabolites, with 22 carbon skeletons, representing monoterpenes, 49 sesquiterpenes, 49-51 diterpenes, 52,53 sesterterpenes 54 and degraded sesterterpenoids 51,55 and diterpenoids 53,56 have been isolated from C. luteomarginata. 57 Examples of the sequestered metabolites are glaciolide (9) 56 and cadlinolide A (10) 53 from the sponge Aplysilla glacialis, and ansellone A (11) 54 from a prey sponge of the Phorbas genus. Their ecological roles are not well dened, 57 but 11 has been shown to be moderately activating towards cellular processes that use the cyclic adenosine monophosphate (cAMP) signal pathway.…”

“…57 Examples of the sequestered metabolites are glaciolide (9) 56 and cadlinolide A (10) 53 from the sponge Aplysilla glacialis, and ansellone A (11) 54 from a prey sponge of the Phorbas genus. Their ecological roles are not well dened, 57 but 11 has been shown to be moderately activating towards cellular processes that use the cyclic adenosine monophosphate (cAMP) signal pathway. 54 Terpenoid biosynthesis in C. luteomarginata was suspected when all previously analysed individuals from a British Columbian (Canadian) study consistently possessed the same three terpenoids.…”

Stereospecific Construction of Contiguous Quaternary All‐Carbon Centers by Oxidative Ring Contraction

“…In this regard, natural products incorporating contiguous quaternary all‐carbon centers are frequently isolated and possess unique structures. Sometimes, both stereoisomers of contiguous quaternary all‐carbon centers are encountered in the same family of natural products (Figure ; e.g., communesin F and perophoramidine, and tochuinyl acetate and herbertenolide).…”

Stereospecific Construction of Contiguous Quaternary All‐Carbon Centers by Oxidative Ring Contraction

“…In this regard, natural products incorporating contiguous quaternary all-carbon centers are frequently isolated and possess unique structures. Sometimes,both stereoisomers of contiguous quaternary allcarbon centers are encountered in the same family of natural products (Figure 1; e.g.,c ommunesin F [1] and perophoramidine, [2] and tochuinyl acetate [3] and herbertenolide [4] ).…”