biostudies-literatureAlvarez-Constantino AMXunta de GaliciaMinisterio de Ciencia e Innovaci?nEuropean Regional Development Fund1185-1193https://www.ebi.ac.uk/biostudies/studies/S-EPMC9872091biostudies-literatureUnknown88(2)The Ru-catalyzed intramolecular oxidative amidation (lactamization) of aromatic alkynylamines with 4-picoline <i>N</i>-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 <i>vs</i> hydroamination.The Journal of organic chemistryChemoselective Ru-Catalyzed Oxidative Lactamization <i>vs</i> Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies.PMC9872091ED431G 2019/03RED2018-102387-TPID2020-118048GB-I00ED431C 2022/27PID2020-116861GB-I00Ujaque GAlvarez-Perez AVarela JASaa CAlvarez-Constantino AMSciortino GfalseChemoselective Ru-Catalyzed Oxidative Lactamization <i>vs</i> Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies.The Ru-catalyzed intramolecular oxidative amidation (lactamization) of aromatic alkynylamines with 4-picoline <i>N</i>-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 <i>vs</i> hydroamination.2023-01-01T00:00:00Z2023 Jan2025-04-19T14:30:51.098Z2025-04-19T14:30:51.098ZS-EPMC98720913657961210.1021/acs.joc.2c02770