Photoredox Product Selectivity Controlled by Persistent Radical Stability

The use of photoredox catalysis for the synthesis of small organic molecules relies on harnessing and converting the energy in visible light to drive reactions. Specifically, photon energy is used to generate radical ion species that can be harnessed through subsequent reaction steps to form a desir...

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Veröffentlicht in:Journal of organic chemistry 2024-10, Vol.89 (19), p.13818-13825
Hauptverfasser: Stevenson, Bernard G., Gironda, Cameron, Talbott, Eric, Prascsak, Amanda, Burnett, Nora L., Kompanijec, Victoria, Nakhamiyayev, Roman, Fredin, Lisa A., Swierk, John R.
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container_end_page 13825
container_issue 19
container_start_page 13818
container_title Journal of organic chemistry
container_volume 89
creator Stevenson, Bernard G.
Gironda, Cameron
Talbott, Eric
Prascsak, Amanda
Burnett, Nora L.
Kompanijec, Victoria
Nakhamiyayev, Roman
Fredin, Lisa A.
Swierk, John R.
description The use of photoredox catalysis for the synthesis of small organic molecules relies on harnessing and converting the energy in visible light to drive reactions. Specifically, photon energy is used to generate radical ion species that can be harnessed through subsequent reaction steps to form a desired product. Cyanoarenes are widely used as arylating agents in photoredox catalysis because of their stability as persistent radical anions. However, there are marked, unexplained variations in product yields when using different cyanoarenes. In this study, the quantum yield and product yield of an α-aminoarylation photoredox reaction between five cyanoarene coupling partners and N-phenylpyrrolidine were characterized. Significant discrepancies in cyanoarene consumption and product yield suggested a chemically irreversible, unproductive pathway in the reaction. Analysis of the side products in the reaction demonstrated the formation of species consistent with radical anion fragmentation. Electrochemical and computational methods were used to study the fragmentation of the different cyanoarenes and revealed a correlation between product yield and cyanoarene radical anion stability. Kinetic modeling of the reaction demonstrates that cross-coupling selectivity between N-phenylpyrrolidine and the cyanoarene is controlled by the same phenomenon present in the persistent radical effect.
doi_str_mv 10.1021/acs.joc.3c00490
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Electrochemical and computational methods were used to study the fragmentation of the different cyanoarenes and revealed a correlation between product yield and cyanoarene radical anion stability. 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title Photoredox Product Selectivity Controlled by Persistent Radical Stability
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