4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters

[Image: see text] A novel, metal-free aerobic oxidation method is described. 4-Dimethylaminopyridine (DMAP) successfully catalyzed the oxidation of aryl α-halo esters to corresponding aryl α-keto esters (up to 95% yield) under mild reaction conditions (Li(2)CO(3), dimethylacetamide, air, and room te...

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Autores principales: Jung, Yeonghun, Hong, Jee Eun, Baek, Seung Tae, Hong, Suckchang, Kwak, Jae-Hwan, Park, Yohan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7495759/
https://www.ncbi.nlm.nih.gov/pubmed/32954144
http://dx.doi.org/10.1021/acsomega.0c02511
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author Jung, Yeonghun
Hong, Jee Eun
Baek, Seung Tae
Hong, Suckchang
Kwak, Jae-Hwan
Park, Yohan
author_facet Jung, Yeonghun
Hong, Jee Eun
Baek, Seung Tae
Hong, Suckchang
Kwak, Jae-Hwan
Park, Yohan
author_sort Jung, Yeonghun
collection PubMed
description [Image: see text] A novel, metal-free aerobic oxidation method is described. 4-Dimethylaminopyridine (DMAP) successfully catalyzed the oxidation of aryl α-halo esters to corresponding aryl α-keto esters (up to 95% yield) under mild reaction conditions (Li(2)CO(3), dimethylacetamide, air, and room temperature). A mechanism has been proposed where the oxidation proceeds through a [3 + 2] cycloaddition between O(2) in an air atmosphere and pyridinium ylides. The ylides are supposedly generated from aryl α-halo esters and DMAP in the presence of carbonates. Based on the plausible mechanism, the potential of DMAP as a catalyst in oxidation reactions was extended.
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spelling pubmed-74957592020-09-18 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters Jung, Yeonghun Hong, Jee Eun Baek, Seung Tae Hong, Suckchang Kwak, Jae-Hwan Park, Yohan ACS Omega [Image: see text] A novel, metal-free aerobic oxidation method is described. 4-Dimethylaminopyridine (DMAP) successfully catalyzed the oxidation of aryl α-halo esters to corresponding aryl α-keto esters (up to 95% yield) under mild reaction conditions (Li(2)CO(3), dimethylacetamide, air, and room temperature). A mechanism has been proposed where the oxidation proceeds through a [3 + 2] cycloaddition between O(2) in an air atmosphere and pyridinium ylides. The ylides are supposedly generated from aryl α-halo esters and DMAP in the presence of carbonates. Based on the plausible mechanism, the potential of DMAP as a catalyst in oxidation reactions was extended. American Chemical Society 2020-09-02 /pmc/articles/PMC7495759/ /pubmed/32954144 http://dx.doi.org/10.1021/acsomega.0c02511 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Jung, Yeonghun
Hong, Jee Eun
Baek, Seung Tae
Hong, Suckchang
Kwak, Jae-Hwan
Park, Yohan
4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title_full 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title_fullStr 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title_full_unstemmed 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title_short 4-Dimethylaminopyridine-Catalyzed Metal-Free Aerobic Oxidation of Aryl α-Halo Esters to Aryl α-Keto Esters
title_sort 4-dimethylaminopyridine-catalyzed metal-free aerobic oxidation of aryl α-halo esters to aryl α-keto esters
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7495759/
https://www.ncbi.nlm.nih.gov/pubmed/32954144
http://dx.doi.org/10.1021/acsomega.0c02511
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