Heinz, ChristophCramer, Nicolai2015-09-012015-09-01201510.1021/jacs.5b07964https://infoscience.epfl.ch/handle/20.500.14299/117507WOS:000361251600019Fijiolide A is a secondary metabolite isolated from a marine-derived actinomycete and displays inhibitory activity against TNF-α-induced activation of NFκB, an important transcription factor and a potential target for the treatment of different cancers and inflammation related diseases. Fijiolide A is a glycosylated complex paracyclophane, which is structurally closely related to the Bergman-aromatization product of enediyne C-1027. We report an enantioselective synthesis offijiolide A demonstrating the power of fully intermolecular ruthenium-catalyzed [2 + 2 + 2] cyclotrimerizations with three different alkynes to assemble the heavily substituted central arene core. The characteristic strained [2.6]-paracyclophane structure is accessed by a templated atropselective macroetherification reaction.text::journal::journal article::research article