American Chemical Society
sc3c04938_si_001.pdf (7.21 MB)

Liquid-Assisted Grinding Accelerating the Defluorinative Coupling of gem-Difluoroalkenes under Ball-Milling Conditions

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journal contribution
posted on 2023-12-15, 17:47 authored by Jiajia Jia, Qianqian Wang, Junyang Li, Zhiwei Xu, Heng Li, Donghui Wei, Bingxin Yuan
We disclose a rapid and versatile mechanochemical method coupling gem-difluoroalkenes with thiols, yielding Z-selective monofluorovinyl sulfides. Operating solvent-free, the reaction completes within 30 s, accommodating various nucleophiles (P, N, and O) and overcoming F-elimination to provide α, α-difluoroalkylthioethers under base-free conditions. Mechanistic investigations indicate that the base DBU abstracts a proton from the thiol, with the formation of Z-configuration being slightly more energetically favorable in kinetics. The protocol demonstrates good scalability, achieving gram-scale production with consistent Z-selectivity.