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Porphyrins as Photoredox Catalysts: Experimental and Theoretical Studies

Rybicka-Jasińska, Katarzyna, Shan, Wenqian, Zawada, Katarzyna, Kadish, Karl M., Gryko, Dorota
Journal of the American Chemical Society 2016 v.138 no.47 pp. 15451-15458
aldehydes, catalysts, catalytic activity, diazo compounds, electrochemistry, electron transfer, energy transfer, irradiation, photosensitizing agents, porphyrins, singlet oxygen
Metalloporphyrins not only are vital in biological systems but also are valuable catalysts in organic synthesis. On the other hand, catalytic properties of free base porphyrins have been less explored. They are mostly known as efficient photosensitizers for the generation of singlet oxygen via photoinduced energy transfer processes, but under light irradiation, they can also participate in electron transfer processes. Indeed, we have found that free base tetraphenylporphyrin (H₂TPP) is an efficient photoredox catalyst for the reaction of aldehydes with diazo compounds leading to α-alkylated derivatives. The performance of a porphyrin catalyst can be optimized by tailoring various substituents at the periphery of the macrocycle at both the β and meso positions. This allows for the fine tuning of their optical and electrochemical properties and hence their catalytic activity.