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

[Image: see text] 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)...

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Autores principales: Álvarez-Constantino, Andrés M., Álvarez-Pérez, Andrea, Varela, Jesús A., Sciortino, Giuseppe, Ujaque, Gregori, Saá, Carlos
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9872091/
https://www.ncbi.nlm.nih.gov/pubmed/36579612
http://dx.doi.org/10.1021/acs.joc.2c02770
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author Álvarez-Constantino, Andrés M.
Álvarez-Pérez, Andrea
Varela, Jesús A.
Sciortino, Giuseppe
Ujaque, Gregori
Saá, Carlos
author_facet Álvarez-Constantino, Andrés M.
Álvarez-Pérez, Andrea
Varela, Jesús A.
Sciortino, Giuseppe
Ujaque, Gregori
Saá, Carlos
author_sort Álvarez-Constantino, Andrés M.
collection PubMed
description [Image: see text] 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.
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spelling pubmed-98720912023-01-25 Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies Álvarez-Constantino, Andrés M. Álvarez-Pérez, Andrea Varela, Jesús A. Sciortino, Giuseppe Ujaque, Gregori Saá, Carlos J Org Chem [Image: see text] 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. American Chemical Society 2022-12-29 /pmc/articles/PMC9872091/ /pubmed/36579612 http://dx.doi.org/10.1021/acs.joc.2c02770 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Álvarez-Constantino, Andrés M.
Álvarez-Pérez, Andrea
Varela, Jesús A.
Sciortino, Giuseppe
Ujaque, Gregori
Saá, Carlos
Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title_full Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title_fullStr Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title_full_unstemmed Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title_short Chemoselective Ru-Catalyzed Oxidative Lactamization vs Hydroamination of Alkynylamines: Insights from Experimental and Density Functional Theory Studies
title_sort chemoselective ru-catalyzed oxidative lactamization vs hydroamination of alkynylamines: insights from experimental and density functional theory studies
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9872091/
https://www.ncbi.nlm.nih.gov/pubmed/36579612
http://dx.doi.org/10.1021/acs.joc.2c02770
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