Dehydroxy-Perfluoro-tert-butylation of alcohols with PhSO2C(CF3)3 and insights into the structure of the [C(CF3)3]− anion

Kaidi Zhu, Qinyu Luo, Pengcheng Xu, Zhigang Ni, Shuo Sun, Mingyou Hu, Chuanfa Ni and Jinbo Hu ()
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Kaidi Zhu: 345 Ling-Ling Road
Qinyu Luo: 345 Ling-Ling Road
Pengcheng Xu: 345 Ling-Ling Road
Zhigang Ni: 2318 Yuhangtang Road
Shuo Sun: 345 Ling-Ling Road
Mingyou Hu: 345 Ling-Ling Road
Chuanfa Ni: 345 Ling-Ling Road
Jinbo Hu: 345 Ling-Ling Road

Nature Communications, 2025, vol. 16, issue 1, 1-9

Abstract: Abstract Branched PFOA and PFOS have shorter half-lives, lower toxicity, and weaker serum protein binding than linear ones, offering better environmental and health safety. Yet methods to access such branched motifs remain under developed. We now introduce a one-step dehydroxy-perfluoro-tert-butylation of alcohols, in which perfluoro-tert-butyl phenyl sulfone serves both to activate the C–O bond and to deliver the perfluoro-tert-butyl group. Mechanistic studies—including DFT calculations—reveal that perfluoro-tert-butyl phenyl sulfone first generates perfluoroisobutylene in situ to effect C–O bond cleavage, after which a catalytic iodide engages in the C–C bond-forming event. Remarkably, the isolated perfluoro-tert-butyl anion salt, characterized by single-crystal X-ray diffraction, displays significant negative hyperconjugation, as evidenced by the elongated C–F bonds. This operationally simple protocol tolerates a wide array of functional groups and complex substrates, providing rapid access to branched perfluoroalkyl scaffolds with broad implications for drug discovery and advanced materials.

Date: 2025
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DOI: 10.1038/s41467-025-63180-0

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