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Insights into the role of graphitic carbon nitride as a photobase in proton-coupled electron transfer in (sp3)C‒H oxygenation of oxazolidinones

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Galushchinskiy,  Alexey       
Aleksandr Savateev, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Savateev,  Aleksandr       
Aleksandr Savateev, Kolloidchemie, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Citation

Galushchinskiy, A., Zou, Y., Odutola, J., Nikačević, P., Shi, J.-W., Tkachenko, N., et al. (2023). Insights into the role of graphitic carbon nitride as a photobase in proton-coupled electron transfer in (sp3)C‒H oxygenation of oxazolidinones. Angewandte Chemie International Edition. doi:10.1002/anie.202301815.


Cite as: https://hdl.handle.net/21.11116/0000-000A-F30C-7
Abstract
Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is more favorable pathway for substrates possessing X‒H bonds. Upon excitation of an (sp2)N-rich structure of g-CN with visible light, it behaves as a photobase – undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modelling allowed us to identify active sites for PCET – the ‘triangular pockets’ on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to cleave selectively endo-(sp3yond in oxazolidine-2-ones followed by trapping the radical with O2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of apparent pKa value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) ~100 kcal mol-1.