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Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow

Although carbon dioxide (CO(2)) is highly abundant, its low reactivity has limited its use in chemical synthesis. In particular, methods for carbon–carbon bond formation generally rely on two-electron mechanisms for CO(2) activation and require highly activated reaction partners. Alternatively, radi...

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Autores principales: Seo, Hyowon, Katcher, Matthew H., Jamison, Timothy F.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5407320/
https://www.ncbi.nlm.nih.gov/pubmed/28430203
http://dx.doi.org/10.1038/nchem.2690
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author Seo, Hyowon
Katcher, Matthew H.
Jamison, Timothy F.
author_facet Seo, Hyowon
Katcher, Matthew H.
Jamison, Timothy F.
author_sort Seo, Hyowon
collection PubMed
description Although carbon dioxide (CO(2)) is highly abundant, its low reactivity has limited its use in chemical synthesis. In particular, methods for carbon–carbon bond formation generally rely on two-electron mechanisms for CO(2) activation and require highly activated reaction partners. Alternatively, radical pathways accessed via photoredox catalysis could provide new reactivity under milder conditions. Here we demonstrate the direct coupling of CO(2) and amines via the single-electron reduction of CO(2) for the photoredox-catalyzed, continuous flow synthesis of α-amino acids. By leveraging advantages for utilizing gases and photochemistry in flow, a commercially available organic photoredox catalyst effects the selective α-carboxylation of amines bearing various functional groups and heterocycles. Preliminary mechanistic studies support CO(2) activation and carbon–carbon bond formation via single-electron pathways, and we expect that this strategy will inspire new perspectives on using this feedstock chemical in organic synthesis.
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spelling pubmed-54073202017-06-26 Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow Seo, Hyowon Katcher, Matthew H. Jamison, Timothy F. Nat Chem Article Although carbon dioxide (CO(2)) is highly abundant, its low reactivity has limited its use in chemical synthesis. In particular, methods for carbon–carbon bond formation generally rely on two-electron mechanisms for CO(2) activation and require highly activated reaction partners. Alternatively, radical pathways accessed via photoredox catalysis could provide new reactivity under milder conditions. Here we demonstrate the direct coupling of CO(2) and amines via the single-electron reduction of CO(2) for the photoredox-catalyzed, continuous flow synthesis of α-amino acids. By leveraging advantages for utilizing gases and photochemistry in flow, a commercially available organic photoredox catalyst effects the selective α-carboxylation of amines bearing various functional groups and heterocycles. Preliminary mechanistic studies support CO(2) activation and carbon–carbon bond formation via single-electron pathways, and we expect that this strategy will inspire new perspectives on using this feedstock chemical in organic synthesis. 2016-12-26 2017-05 /pmc/articles/PMC5407320/ /pubmed/28430203 http://dx.doi.org/10.1038/nchem.2690 Text en Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:http://www.nature.com/authors/editorial_policies/license.html#terms Reprints and permissions information is available at www.nature.com/reprints (http://www.nature.com/reprints) .
spellingShingle Article
Seo, Hyowon
Katcher, Matthew H.
Jamison, Timothy F.
Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title_full Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title_fullStr Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title_full_unstemmed Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title_short Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
title_sort photoredox activation of carbon dioxide for amino acid synthesis in continuous flow
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5407320/
https://www.ncbi.nlm.nih.gov/pubmed/28430203
http://dx.doi.org/10.1038/nchem.2690
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