Premium
Innovative Syntheses of Cyano(fluoro)borates: Catalytic Cyanation, Electrochemical and Electrophilic Fluorination
Author(s) -
Drisch Michael,
Bischoff Lisa A.,
Sprenger Jan A. P.,
Hennig Philipp T.,
Wirthensohn Raphael,
Landmann Johannes,
Konieczka Szymon Z.,
Hailmann Michael,
Ignat'ev Nikolai V.,
Finze Maik
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002324
Subject(s) - electrophilic fluorination , cyanation , trimethylsilyl cyanide , chemistry , boron trifluoride , halogenation , cyanide , yield (engineering) , electrophile , catalysis , lewis acids and bases , fluorine , electrosynthesis , alkali metal , boron , trimethylsilyl , electrochemistry , organic chemistry , inorganic chemistry , materials science , metallurgy , electrode
Different types of high‐yield, easily scalable syntheses for cyano(fluoro)borates Kt[BF n (CN) 4− n ] ( n= 0–2) (Kt=cation), which are versatile building blocks for materials applications and chemical synthesis, have been developed. Tetrafluoroborates react with trimethylsilyl cyanide in the presence of metal‐free Brønsted or Lewis acid catalysts under unprecedentedly mild conditions to give tricyanofluoroborates or tetracyanoborates. Analogously, pentafluoroethyltrifluoroborates are converted into pentafluoroethyltricyanoborates. Boron trifluoride etherate, alkali metal salts, and trimethylsilyl cyanide selectively yield dicyanodifluoroborates or tricyanofluoroborates. Fluorination of cyanohydridoborates is the third reaction type that includes direct fluorination with, for example, elemental fluorine, stepwise halogenation/fluorination reactions, and electrochemical fluorination (ECF) according to the Simons process. In addition, fluorination of [BH(CN) 2 {OC(O)Et}] − to result in [BF(CN) 2 {OC(O)Et}] − is described.