DOI: 10.1002/chem.202302701 ISSN:

Synthesis of Partially Fluorinated Alkyl Triflates via Electrochemical Fluorination (Simons Process)

Tanja Knuplez, Leon Schneider, Tobias Preitschopf, Younes Bejaoui, Ludwig Zapf, Nils Schopper, Kristina Maibom, Jan Sprenger, Franziska Gehrke, Sabine Lorenzen, Roland Graf, Rüdiger Bertermann, Ingo Fischer, Nikolai Ignat’ev, Maik Finze
  • General Chemistry
  • Catalysis
  • Organic Chemistry

A scalable straightforward synthesis of monofluoro‐ and difluoro­methyl ­triflate CF3SO2OCH2F (MH2F) and CF3SO2OCHF2 (MHF2) via electrochemical fluorination (Simons process, ECF) of methyl triflate MH3 in anhydrous hydrogen fluoride at nickel anodes is pre­sent­ed. The ECF method is also feasible for the preparation of the deuterated analogues CF3SO2OCD2F (MD2F) and CF3SO2OCDF2 (MD2F). Surprisingly, no H/D exchange occurs during ECF of CF3SO2OCD3 (MD3), which provides further evidence for a NiF3/NiF4‐mediated ECF mechanism. The ECF of selected partially fluorinated ethyl triflates is described and electro­chemical fluorination of CF3SO2­O­CH2CF3 (EH2F3) leads to the so far unknown chiral CF3SO2­OCHFCF3 (EHFF3). The analogous fluoromethyl and fluoroethyl nonaflates are also accessible via ECF. The present study contains detailed spec­tros­copic, structural, and thermal data on (fluoro)methyl and fluoro(ethyl) triflates.

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