Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies

Autor: Andrés M. Álvarez-Constantino, Andrea Álvarez-Pérez, Jesús A. Varela, Giuseppe Sciortino, Gregori Ujaque, Carlos Saá
Přispěvatelé: Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares, Universidade de Santiago de Compostela. Departamento de Química Orgánica
Jazyk: angličtina
Rok vydání: 2023
Předmět:
Popis: The 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. This work has received financial support from MICINN (projects PID2020-118048GB-I00, PID2020-116861GB-I00, and ORFEO-CINQA network RED2018-102387-T), the Xunta de Galicia (project ED431C 2022/27, Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03), and the European Union (European Regional Development Fund) SI
Databáze: OpenAIRE