Zinc-Catalyzed Cyclization of Alkynyl Derivatives: Substrate Scope and Mechanistic Insights Martínez de Sarasa Buchaca, Marc Gaona, Miguel A. Sánchez-Barba, Luis F. Garcés, Andrés Rodríguez, Ana M. Rodríguez Diéguez, Antonio de la Cruz-Martínez, Felipe Castro-Osma, José A. Lara Sanchez, Agustín Novel alkyl zinc complexes supported by acetamidate/ thioacetamidate heteroscorpionate ligands have been successfully synthesized and characterized. These complexes exhibited different coordination modes depending on the electronic and steric effects of the acetamidate/thioacetamidate moiety. Their catalytic activity has been tested toward the hydroelementation reactions of alkynyl alcohol/acid substrates, affording the corresponding enol ether/unsaturated lactone products under mild reaction conditions. Kinetic studies have been performed and confirmed that reactions are first-order in [catalyst] and zero-order in [alkynyl substrate]. DFT calculations supported a reaction mechanism through the formation of the catalytically active species, an alkoxide-zinc intermediate, by a protonolysis reaction of the Zn−alkyl bond with the alcohol group of the substrate. Based on the experimental and theoretical results, a catalytic cycle has been proposed. 2024-07-31T10:45:35Z 2024-07-31T10:45:35Z 2024-07-16 journal article Martínez de Sarasa Buchaca, M. et. al. Inorg. Chem. 2024, 63, 13875−13885. [https://doi.org/10.1021/acs.inorgchem.4c00832] https://hdl.handle.net/10481/93701 10.1021/acs.inorgchem.4c00832 eng http://creativecommons.org/licenses/by/4.0/ open access Atribución 4.0 Internacional ACS Publications