Direct trifluoro-methoxylation of aromatics with perfluoro-methyl-hypofluorite

Mechanistic studies on intramolecular C–H trifluoromethoxylation of (hetero)arenes via OCF3-migration

“…10 Over the past few decades, there have been a number of synthetic routes towards trifluoromethoxylated (hetero)arenes: (i) chlorine-fluorine exchange on (hetero)aryl trichloromethyl ethers; 11 (ii) deoxyfluorination of phenol fluoroformates; 12 (iii) oxidative desulfurization-fluorination of aryl dithiocarbonates (xanthogenates); 13 (iv) electrophilic trifluoromethylation of phenols; 14 (v) nucleophilic trifluoromethoxylation of benzyne; 15 (vi) silver-mediated trifluoromethoxylation of aryl stannanes and aryl boronic acids; 16 (vii) radical trifluoromethoxylation; 17 and (viii) silver-mediated trifluoromethylation of phenols. 18 However, most of these approaches suffer from poor substrate scope and functional group tolerance, require the use of highly toxic, corrosive and/or temperature sensitive reagents, or impractical reaction conditions.…”

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

“…Synthese von Aryltrifluormethylethern Nucleophile Fluorierungen von Aryltrichlormethylethern, [461] Arylchlorthionoformiaten, [461b, 462] Phenylfluorformiaten [463] und Arylxanthaten [464] sind die häufigsten Synthesemethoden für Trifluormethyloxyarene. [471] 6.1. Aryltrichlormethylether, [461b,d] Die Verwendung des Trifluormethoxid-Anions zur Bildung der Aryl-C-O-Bindung ist noch nicht so gut untersucht wie andere Methoden.…”

Direct fluorination of carbon monoxide in microreactors

“…In general the reaction of organic substances with fluorine, in conventional reactors, is difficult to control due to the heat generated by the reaction itself [11]. The fluorination of a hydrogenated compound is a typical example where the exothermicity of the whole reaction is such that any carbon-carbon bond can be easily broken if the reaction is not properly controlled by dilution of reagents and by adopting a low reaction temperature and CH activation [12,13]. The improperly conducted fluorination leads invariably to several byproducts and ultimately to CF 4 and HF [14].…”