Velasco Rubio, ÁlvaroBernárdez Alfaya, RodrigoVarela Carrete, Jesús ÁngelSaá Rodríguez, Carlos2022-08-082022-08-082021J. Org. Chem. 2021, 86, 10889−10902. https://doi.org/10.1021/acs.joc.1c012680022-3263http://hdl.handle.net/10347/29033Benzofused seven-membered heterocycles such as 1,4-benzo[e]diazepines (1,4-BZDs) and 1,4-benzo[e]oxazepines (1,4-BZOs) were efficiently synthesized by Rh-catalyzed hydrofunctionalization of internal alkynes and allenes in good to excellent yields. The asymmetric hydroamination of (aminomethyl)anilines gave rise to 3-vinyl-1,4-BZDs with excellent enantioselectivities. Orthogonal N-deprotection of 1,4-BZDs allowed an easy entry to an advanced pyrrolobenzodiazepine metabolite of the V2-receptor antagonist LixivaptanengAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/AllenesHydrocarbonsLayersLipidsMixturesjournal article10.1021/acs.joc.1c01268open access