Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis

The reaction of [{(ArNCMe)(2)CH}Al] (Ar = 2,6-di-iso-propylphenyl) with aryl methyl ethers proceeded with alumination of the sp(3) C–O bond. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy(3))(2)], chemoselective sp(2) C–O bond functionalisat...

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Autores principales: Brown, Ryan K., Hooper, Thomas N., Rekhroukh, Feriel, White, Andrew J. P., Costa, Paulo J., Crimmin, Mark R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8567294/
https://www.ncbi.nlm.nih.gov/pubmed/34672313
http://dx.doi.org/10.1039/d1cc05408b
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author Brown, Ryan K.
Hooper, Thomas N.
Rekhroukh, Feriel
White, Andrew J. P.
Costa, Paulo J.
Crimmin, Mark R.
author_facet Brown, Ryan K.
Hooper, Thomas N.
Rekhroukh, Feriel
White, Andrew J. P.
Costa, Paulo J.
Crimmin, Mark R.
author_sort Brown, Ryan K.
collection PubMed
description The reaction of [{(ArNCMe)(2)CH}Al] (Ar = 2,6-di-iso-propylphenyl) with aryl methyl ethers proceeded with alumination of the sp(3) C–O bond. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy(3))(2)], chemoselective sp(2) C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp(2) C–O bond to a Pd–Al intermetallic complex.
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spelling pubmed-85672942021-11-09 Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis Brown, Ryan K. Hooper, Thomas N. Rekhroukh, Feriel White, Andrew J. P. Costa, Paulo J. Crimmin, Mark R. Chem Commun (Camb) Chemistry The reaction of [{(ArNCMe)(2)CH}Al] (Ar = 2,6-di-iso-propylphenyl) with aryl methyl ethers proceeded with alumination of the sp(3) C–O bond. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy(3))(2)], chemoselective sp(2) C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp(2) C–O bond to a Pd–Al intermetallic complex. The Royal Society of Chemistry 2021-10-12 /pmc/articles/PMC8567294/ /pubmed/34672313 http://dx.doi.org/10.1039/d1cc05408b Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Brown, Ryan K.
Hooper, Thomas N.
Rekhroukh, Feriel
White, Andrew J. P.
Costa, Paulo J.
Crimmin, Mark R.
Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title_full Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title_fullStr Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title_full_unstemmed Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title_short Alumination of aryl methyl ethers: switching between sp(2) and sp(3) C–O bond functionalisation with Pd-catalysis
title_sort alumination of aryl methyl ethers: switching between sp(2) and sp(3) c–o bond functionalisation with pd-catalysis
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8567294/
https://www.ncbi.nlm.nih.gov/pubmed/34672313
http://dx.doi.org/10.1039/d1cc05408b
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