Sustainable Photoinduced Difunctionalization of Olefins

Keywords

dual catalysis - recyclable system - photomediated process - heteroarenes - olefins

Significance

Difunctionalization of olefins through initial addition of methoxycarbonyl radicals provides an opportunity for rapidly increasing molecular complexity from readily available feedstock materials. While photoredox-based approaches have been promoted as a sustainable methodology to achieve this, one of the drawbacks is these often typically use homogeneous iridium/ruthenium-based catalysts, which must be separated from the desired reaction products. The current report describes the use of graphite carbon nitride (g-C₃N₄) as a recyclable, heterogeneous photocatalyst and its use in conjunction with an iodide salt in the difunctionalization of alkenes with heteroarenes and methyl carbazate.

 

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Comment

Model studies on the reaction between 1-pentene, methyl carbazate and quinoxalinone highlighted that both g-C₃N₄ and an iodide salt were critical for the reaction to occur with acetonitrile shown to be the optimal solvent, while O₂ from air serves as the sole oxidant. Styrenes along with terminal and cyclic olefins were effective substrates, with a broad range of heteroarenes also tolerated by the process. The protocol was also applied to the late-stage functionalization of a series of bioactive molecules, while mechanistic studies suggest that the reaction proceeds through the intermediacy of iodine and superoxide radicals.

 

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Publikationsverlauf

Artikel online veröffentlicht:
23. Juni 2025