open access

https://hdl.handle.net/2115/97468

Defluorinative C-O Coupling between Trifluoromethylarenes and Alcohols via Copper Photoredox Catalysis

英語

photocatalysis

2025-01-22

Wiley-Blackwell

Angewandte chemie-international edition

64(8)

e202419591

Fluorine-containing compounds have shown unparalleled impacts in the realm of functional molecules, and the ability to prepare novel structures has been crucial in unlocking new properties for applications in pharmaceutical and materials science. Herein, we report a copper-catalyzed, photoinduced defluorinative C-O coupling between trifluoromethylarenes and alcohols. This method allows for direct access to a wide selection of difluorobenzylether (ArCF2OR) molecules, including a compound displaying liquid crystal behavior. Through slight modification of the protocol, we were able to generate difluorobenzyliodide (ArCF2I) products, another class of synthetically useful fluorine-bearing molecules. Mechanistic investigations first suggested that ArCF2I can serve as a reservoir to steadily supply the key ArCF2 & sdot; radical species. Furthermore, experimental evidence supported a mechanism consisting of two collaborative cycles: C-F activation operated by a homoleptic Cu(I) coordinated by two bisphosphine ligands as the photocatalyst and C-O coupling promoted by a Cu(I) ligated by a single bisphosphine ligand. The critical roles of the two salt additives, lithium iodide and zinc acetate, in orchestrating the two cycles were also elucidated. This dual-role copper catalyst demonstrates the power of base metal photoredox catalysis in achieving both substrate activation and chemical bond formation via a single catalytic system.

学術雑誌論文

Accepted Manuscript

This is the peer reviewed version of the following article: P. Saha, M. Jin, D. C.-Y. Huang, Angew. Chem. Int. Ed. 2025, 64, e202419591., which has been published in final form at https://doi.org/10.1002/anie.202419591. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.

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