Issue 29, 2025

Difluoroenol phosphinates as difluoroenolate surrogates: synthesis and applications in defluorination and deoxygenative coupling

Abstract

We report defluorinative and deoxygenative functionalization reactions of trifluoromethyl ketones mediated by the phospha-Brook rearrangement, offering a streamlined approach to selectively modifying fluorinated compounds. Trifluoromethyl ketones react with phosphine oxides to undergo a phospha-Brook rearrangement followed by β-fluoride elimination, providing difluoromethyl ketones in good yields. By tuning the reaction conditions, we achieved the selective one-pot synthesis of monofluoromethyl ketones and methyl ketones, demonstrating the method's versatility across a range of fluorine-containing derivatives. Furthermore, we successfully demonstrated a range of deoxygenative transformations of key intermediates, such as difluoroenol phosphinates, showcasing their potential as building blocks for diverse functionalizations. These findings not only expand the synthetic toolbox for fluorine-containing molecules but also highlight the utility of phosphinate intermediates in developing novel reaction pathways.

Graphical abstract: Difluoroenol phosphinates as difluoroenolate surrogates: synthesis and applications in defluorination and deoxygenative coupling

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Article information

Article type
Edge Article
Submitted
29 May 2025
Accepted
20 Jun 2025
First published
20 Jun 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2025,16, 13390-13400

Difluoroenol phosphinates as difluoroenolate surrogates: synthesis and applications in defluorination and deoxygenative coupling

M. B. Kurosawa, S. Shimoyama, H. Tanaka and J. Yamaguchi, Chem. Sci., 2025, 16, 13390 DOI: 10.1039/D5SC03915K

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