Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations

Various substituted bis-(aryl)manganese species were prepared from aryl bromides by one-pot insertion of magnesium turnings in the presence of LiCl and in situ trans-metalation with MnCl(2) in THF at −5 °C within 2 h. These bis-(aryl)manganese reagents undergo smooth iron-catalyzed cross-couplings u...

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Autores principales: Rousseau, Lidie, Desaintjean, Alexandre, Knochel, Paul, Lefèvre, Guillaume
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2020
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7037184/
https://www.ncbi.nlm.nih.gov/pubmed/32046047
http://dx.doi.org/10.3390/molecules25030723
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author Rousseau, Lidie
Desaintjean, Alexandre
Knochel, Paul
Lefèvre, Guillaume
author_facet Rousseau, Lidie
Desaintjean, Alexandre
Knochel, Paul
Lefèvre, Guillaume
author_sort Rousseau, Lidie
collection PubMed
description Various substituted bis-(aryl)manganese species were prepared from aryl bromides by one-pot insertion of magnesium turnings in the presence of LiCl and in situ trans-metalation with MnCl(2) in THF at −5 °C within 2 h. These bis-(aryl)manganese reagents undergo smooth iron-catalyzed cross-couplings using 10 mol% Fe(acac)(3) with various functionalized alkenyl iodides and bromides in 1 h at 25 °C. The aryl-alkenyl cross-coupling reaction mechanism was thoroughly investigated through paramagnetic (1)H-NMR, which identified the key role of tris-coordinated ate-iron(II) species in the catalytic process.
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spelling pubmed-70371842020-03-11 Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations Rousseau, Lidie Desaintjean, Alexandre Knochel, Paul Lefèvre, Guillaume Molecules Article Various substituted bis-(aryl)manganese species were prepared from aryl bromides by one-pot insertion of magnesium turnings in the presence of LiCl and in situ trans-metalation with MnCl(2) in THF at −5 °C within 2 h. These bis-(aryl)manganese reagents undergo smooth iron-catalyzed cross-couplings using 10 mol% Fe(acac)(3) with various functionalized alkenyl iodides and bromides in 1 h at 25 °C. The aryl-alkenyl cross-coupling reaction mechanism was thoroughly investigated through paramagnetic (1)H-NMR, which identified the key role of tris-coordinated ate-iron(II) species in the catalytic process. MDPI 2020-02-07 /pmc/articles/PMC7037184/ /pubmed/32046047 http://dx.doi.org/10.3390/molecules25030723 Text en © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Rousseau, Lidie
Desaintjean, Alexandre
Knochel, Paul
Lefèvre, Guillaume
Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title_full Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title_fullStr Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title_full_unstemmed Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title_short Iron-Catalyzed Cross-Coupling of Bis-(aryl)manganese Nucleophiles with Alkenyl Halides: Optimization and Mechanistic Investigations
title_sort iron-catalyzed cross-coupling of bis-(aryl)manganese nucleophiles with alkenyl halides: optimization and mechanistic investigations
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7037184/
https://www.ncbi.nlm.nih.gov/pubmed/32046047
http://dx.doi.org/10.3390/molecules25030723
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