Antarctic ecosystems are exposed to unique environmental characteristics resulting in communities structured both by biotic interactions such as predation and competition, as well as abiotic factors such as seasonality and ice‐scouring. It is important to understand how ecological factors may trigger chemical mechanisms in marine Antarctic organisms as a response for survival. However, very little is known yet about the evolution of chemical compounds in Antarctic organisms. Investigations in chemical ecology have demonstrated over the last several years that defensive metabolites have evolved in numerous representative Antarctic species. This contradicts earlier theories concerning biogeographic variation in predation and chemical defenses. As reviewed here, a number of interesting natural products have been isolated from Antarctic organisms. However, we believe many more are still to be discovered. Currently, many groups such as microorganisms, planktonic organisms and deep‐sea fauna remain almost totally unknown regarding their natural products. Furthermore, for many described compounds, ecological roles have yet to be evaluated. In fact, much of the research carried out to date has been conducted in the laboratory, and only in a few cases in an ecologically relevant context. Therefore, there is a need to extend the experiments to the field, as done in tropical and temperate marine ecosystems, or at least, to test the activity of the chemicals in natural conditions and ecologically meaningful interactions. Defense against predators is always one of the main topics when talking about the roles of natural products in species interactions, but many other interesting aspects, such as competition, chemoattraction, fouling avoidance and ultraviolet (UV) protection, also deserve further attention. In our opinion, challenging future developments are to be expected for Antarctic marine chemical ecology in the years to come.

Ascidians have developed multiple defensive strategies mostly related to physical, nutritional or chemical properties of the tunic. One of such is chemical defense based on secondary metabolites. We analyzed a series of colonial Antarctic ascidians from deep-water collections belonging to the genera Aplidium and Synoicum to evaluate the incidence of organic deterrents and their variability. The ether fractions from 15 samples including specimens of the species A. falklandicum, A. fuegiense, A. meridianum, A. millari and S. adareanum were subjected to feeding assays towards two relevant sympatric predators: the starfish Odontaster validus, and the amphipod Cheirimedon femoratus. All samples revealed repellency. Nonetheless, some colonies concentrated defensive chemicals in internal body-regions rather than in the tunic. Four ascidian-derived meroterpenoids, rossinones B and the three derivatives 2,3-epoxy-rossinone B, 3-epi-rossinone B, 5,6-epoxy-rossinone B, and the indole alkaloids meridianins A–G, along with other minoritary meridianin compounds were isolated from several samples. Some purified metabolites were tested in feeding assays exhibiting potent unpalatabilities, thus revealing their role in predation avoidance. Ascidian extracts and purified compound-fractions were further assessed in antibacterial tests against a marine Antarctic bacterium. Only the meridianins showed inhibition activity, demonstrating a multifunctional defensive role. According to their occurrence in nature and within our colonial specimens, the possible origin of both types of metabolites is discussed.

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Chemical investigation of the lipophilic extract of the Antarctic soft coral Alcyonium grandis led us to the finding of nine unreported sesquiterpenoids, 2-10. These molecules are members of the illudalane class and in particular belong to the group of alcyopterosins, illudalanes isolated from marine organisms. The structures of 2-10 were determined by interpretation of spectroscopic data. Repellency experiments conducted using the omnivorous Antarctic sea star Odontaster validus revealed a strong activity in the lipophilic extract of A. grandis against predation.

Alcyonacean soft corals lack physical or skeletal defenses and their nematocyst system is weak, leading to the conclusion that soft corals mainly rely on chemistry for protection from predators and microbes. Defensive chemicals of primary and secondary metabolic origin are exuded in the mucus surface layer, explaining the general lack of heavy fouling and predation in corals. In Antarctic ecosystems, where generalist predation is intense and mainly driven by invertebrate consumers, the genus Alcyonium is represented by eight species. Our goal was to investigate the understudied chemical ecology of Antarctic Alcyonium soft corals. We obtained six samples belonging to five species: A. antarcticum, A. grandis, A. haddoni, A. paucilobulatum, and A. roseum, and assessed the lipid-soluble fractions for the presence of defensive agents in these specimens. Ethyl ether extracts were tested in feeding bioassays with the sea star Odontaster validus and the amphipod Cheirimedon femoratus as putative sympatric predators. Repellent activities were observed towards both consumers in all but one of the samples assessed. Moreover, three of the extracts caused inhibition to a sympatric marine bacterium. The ether extracts afforded characteristic illudalane sesquiterpenoids in two of the samples, as well as particular wax esters subfractions in all the colonies analyzed. Both kinds of metabolites displayed significant deterrent activities demonstrating their likely defensive role. These results suggest that lipophilic chemicals are a first line protection strategy in Antarctic Alcyonium soft corals against predation and bacterial fouling.

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