Knuplez Tanja, Schneider Leon N, Preitschopf Tobias, Bejaoui Younes K J, Zapf Ludwig, Schopper Nils, Maibom Kristina A M, Sprenger Jan A P, Gehrke Franziska, Lorenzen Sabine, Graf Roland, Bertermann Rüdiger, Fischer Ingo, Ignat'ev Nikolai V, Finze Maik
Institut für nachhaltige Chemie & Katalyse mit Bor (ICB) Institut für Anorganische Chemie, Julius-Maximimilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institut für Physikalische Chemie, Julius-Maximimilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2023 Nov 16;29(64):e202302701. doi: 10.1002/chem.202302701. Epub 2023 Oct 11.
A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF SO OCH F (M ) and CF SO OCHF (M ) through electrochemical fluorination (ECF, Simons process) of methyl triflate M in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF SO OCD F (M ) and CF SO OCDF (M ). Surprisingly, no H/D exchange occurs during ECF of CF SO OCD (M ); this provides further evidence for a NiF /NiF -mediated ECF mechanism. The ECF of selected partially fluorinated ethyl triflates is described, and electrochemical fluorination of CF SO OCH CF (E ) leads to the until now unknown chiral CF SO OCHFCF (E ). The analogous fluoromethyl and fluoroethyl nonaflates are also accessible by ECF. This study contains detailed spectroscopic, structural, and thermal data on (fluoro)methyl and fluoro(ethyl) triflates.
本文介绍了通过在镍阳极上于无水氟化氢中对三氟甲磺酸甲酯（M）进行电化学氟化（ECF，西蒙斯法），可扩展且直接地合成单氟和二氟甲基三氟甲磺酸酯CF₃SO₂OCH₂F（M₁）和CF₃SO₂OCHF₂（M₂）。ECF方法对于制备氘代类似物CF₃SO₂OCD₂F（M₁-d₂）和CF₃SO₂OCDF₂（M₂-d₂）也是可行的。令人惊讶的是，在CF₃SO₂OCD₃（M-d₃）的ECF过程中未发生H/D交换；这为NiF₂/NiF₃介导的ECF机制提供了进一步的证据。描述了所选部分氟化的乙基三氟甲磺酸酯的ECF，并且CF₃SO₂OCH₂CF₃（E₁）的电化学氟化导致了迄今未知的手性CF₃SO₂OCHFCF₃（E₂）。类似的氟甲基和氟乙基九氟甲磺酸酯也可通过ECF获得。本研究包含了关于（氟）甲基和氟（乙基）三氟甲磺酸酯的详细光谱、结构和热数据。
