Álvarez-Constantino, Andrés M.Álvarez Pérez, AndreaVarela Carrete, Jesús ÁngelSciortino, GiuseppeUjaque Pérez, GregoriSaá Rodríguez, Carlos2023-03-172023-03-172023Álvarez-Constantino, A., Álvarez-Pérez, A., Varela, J. A., Sciortino, G., Ujaque, G., Saá, C. (2023). Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies. J. Org. Chem., 88, 2, 1185-1930022-3263http://hdl.handle.net/10347/30334The Ru-catalyzed intramolecular oxidative amidation (lactamization) of aromatic alkynylamines with 4-picoline N-oxide as an external oxidant has been developed. This chemoselective process is very efficient to achieve medium-sized ε- and ζ-lactams (seven- and eight-membered rings) but not for the formation of common δ-lactams (six-membered rings). DFT studies unveiled the capital role of the chain length between the amine and the alkyne functionalities: the longer the connector, the more favored the lactamization process vs hydroamination.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/)AlkynylaminesBenzazepinonesMedium-sized lactamsLactamizationsRuthenium catalystsjournal article10.1021/acs.joc.2c027701520-6904open access