Bello García, JesúsPadín Santos, DamiánVarela Carrete, Jesús ÁngelSaá Rodríguez, Carlos2021-07-292021Bello-García, J., Padín, D., Varela, J. A., Saá, C. (2021). Nonplanar Tub-shaped Benzocyclooctatetraenes via Halogen-Radical Ring Opening of Dihydrobiphenylenes. Org. Lett., 23, 14, 5539-55441523-7060PMC8499027http://hdl.handle.net/10347/26643NOTICE: This is the peer reviewed version of the following article: Bello-García, J., Padín, D., Varela, J. A., Saá, C. (2021). Nonplanar Tub-shaped Benzocyclooctatetraenes via Halogen-Radical Ring Opening of Dihydrobiphenylenes. Org. Lett., 23, 14, 5539-5544. [doi: 10.1021/acs.orglett.1c01881]. This article may be used for non-commercial purposes in accordance with American Chemical Society Terms and Conditions for self-archivingA novel tandem Ru-catalyzed [2 + 2 +2] cycloaddition of arylenynes to dihydrobiphenylenes followed by halogen-radical ring opening has been developed for the construction of tub-shaped halogenated benzocyclooctatetraenes (bCOTs). Cross-couplings and Diels-Alder reactions of the brominated bCOTs allow the formation of the corresponding eight-membered ring fused PAHs. The halogen-radical ring opening prob-ably occurs via a selective formation of a bis-allyl radical at the 1,3-cyclohexadiene moiety, halogenation at the bridgehead carbon and final electrocyclic ring opening.eng© 2021 American Chemical Society. This is an open access article under the CC Attribution 4.0 International (CC BY 4.0) license (http://creativecommons.org/licenses/by/4.0/)CyclooctatetraenesDihydrobiphenylenesCOT-PAHsElectrocyclic ring openingRadical halogenationjournal article10.1021/acs.orglett.1c018811523-7052open access