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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