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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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Detalles Bibliográficos
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
Descripción
Sumario: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.