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Porphyrins as Photoredox Catalysts in Csp²–H Arylations: Batch and Continuous Flow Approaches

de Souza, Aline A. N., Silva, Nathalia S., Müller, Andressa V., Polo, André S., Brocksom, Timothy J., de Oliveira, Kleber T.
Journal of organic chemistry 2018 v.83 no.24 pp. 15077-15086
aldehydes, chemical structure, diazonium compounds, electrochemistry, organic chemistry, photocatalysis, photocatalysts, porphyrins, redox potential, redox reactions, salts
We have investigated both batch and continuous flow photoarylations of enol-acetates to yield different α-arylated aldehyde and ketone building blocks by using diazonium salts as the aryl-radical source. Different porphyrins were used as SET photocatalysts, and photophysical as well as electrochemical studies were performed to rationalize the photoredox properties and suggest mechanistic insights. Notably, the most electron-deficient porphyrin (meso-tetra(pentafluorophenyl)porphyrin) shows the best photoactivity as an electron donor in the triplet excited state, which was rationalized by the redox potentials of excited states and the turnover of the porphyrins in the photocatalytic cycle. A two-step continuous protocol and multigram-scale reactions are also presented revealing a robust, cost-competitive, and easy methodology, highlighting the significant potential of porphyrins as SET photocatalysts.