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Chinese researchers develop light-driven method to generate carbon radicals

The researchers used the method to modify complex natural products, including quinine and paclitaxel.

Researchers at the Shanghai Institute of Organic Chemistry of the Chinese Academy of Sciences have developed a way to generate carbon radicals using visible light. The findings were published in Nature.

Author: Робот Source: Chinese Academy of Sciences

A laboratory vessel illuminated during a chemical reaction
Researchers developed a visible-light method for generating carbon radicals. Illustrative photo. Photo: Kost9n4 / Pixabay, Pixabay Content License

Researchers at the Shanghai Institute of Organic Chemistry of the Chinese Academy of Sciences have developed a method to generate carbon radicals through metal-to-ligand charge transfer (MLCT). The process has potential applications in photocatalysis, organic synthesis and energy conversion.

Without an effective follow-up reaction, conventional MLCT is reversible. To overcome this limitation, the team designed and isolated copper-sulfone complexes. They remain stable in the dark for more than three years at room temperature.

Under visible light, the ligand in the complexes undergoes irreversible fragmentation, producing alkyl radicals. The method can generate both fluorinated and non-fluorinated alkyl radicals, including methyl radicals. The researchers used it to alkylate alkenes, arenes and alkynes.

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The team also developed copper-catalyzed fluoroalkylation reactions for arenes and terminal alkynes. It reported the first efficient and broadly applicable perfluorocyclobutylation reaction.

The method was used for the late-stage modification of complex natural products, including quinine and paclitaxel. Experiments to clarify the mechanism confirmed the formation of Cu(II) species and carbon radicals during the reaction.

The findings were published in Nature. The work was supported by the National Natural Science Foundation of China, the Ministry of Science and Technology and the Chinese Academy of Sciences.

Translated from Chinese using artificial intelligence. Source: Chinese Academy of Sciences

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