Fluoroxytrifluoromethane

Fluoroxytrifluoromethane, a source of electrophilic fluorine, has recently been employed by Barton et al. for the fluorination of unsaturated steroids. ... 

Fluoroxytrifluoromethane (trifluoromethyl hypofluorite) and acetyl hypofluorite are the most commonly used neutral hypofluontes, cesium fluoroxysultate is an inorganic anionic fluoroxy derivative... 

Reactions of fluoroxytrifluoromethane with enol ethers, enol acetates, and enamines [/, 2, 3] are very useful, especially for the preparation of steroidal ct-fluoTo ketones (Table 2, entries 1, 3, 5, 6, and 7) [7] (equation 12)... 

Acetyl hypofluorite is very effective m the fluorination of the aryl-metal (Hg, Ge, or Si) bond, but yields are frequently low. With aryl silicon compounds some competition exists for replacement of an aromatic hydrogen [5i, 52, 55, 54] (equations 25-27). Fluoroxytrifluoromethane fluorinates p-methoxypheny 1 mercuric acetate to givep-fluoroanisole in 86% yield [52]... 

Fluoroxytrifluoromethane, a source of electrophilic fluorine, has recently been employed by Barton et ah for the fluorination of unsaturated steroids.143,144 It is more reactive than perchloryl fluoride and therefore not without danger. It forms, for instance, a highly explosive product with pyridine.143 Like perchloryl fluoride it reacts with enol ethers, esters and enamines, but at lower temperature (— 78°) to yield the fluorinated ketones as well as addition... 

Fluoroxytrifluoromethane is prepared in a process that uses cesium fluoride as a catalyst for the reaction between fluorine and carbon monoxide [73] (equation 1) Bisfluoroxydifluoromethane is prepared in a similar manner from carbon dioxide [73]. Fluoroxymethane was prepared recently [74]... 

The /V-fluoroamide reactants were initially prepared by fluormation of amides with fluoroxytrifluoromethane [63 Current methods involve the direct fluorination of amide reagents with elemental fluorine under a variety of conditions [48, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 76, 81, 82] (Tables 3a and 3b)... 

The ion-pair formation is preceded by an initial equilibrium, which quickly leads to a perpendicular tt complex (Scheme 23). A similar reaction pathway is reported for the reactions of iodine (and bromine) monofluorides107,108. Also, the addition of fluoroxytrifluoromethane CF3OF to both cis- and fraws-stilbenes109 enables a syn addition... 

ElectropMBc fluorinatian. Barton et al. have examined a number of fluoroxy reagents as electrophilic fluorinating agents, and conclude that bis(fluoroxy)difluoro-methane is as useful as fluoroxytrifluoromethane (2, 200 3, 146-147) and is potentially cheaper. 

Fittorimted steroids. The action of fluoroxytrifluoromethane on the enol acetates of 3-keto-A4- and 3-keto-A Astcroids yields derivatives fluorinated at the 6- and 2-positions, respectively. ... 

Reactions of Enol Derivatives and Enamines.—Enolic acetates are transformed into fluoro-ketones by the action of fluoroxytrifluoromethane, a source of electrophilic fluorine (Scheme 10)/ Peroxylauric acid reacted with the enol... 

Fluorine and fluoroxytrifluoromethane were found to fluorinate tertiary carbon atoms in the liquid phase in halogenated solvents (CH2CI2, CHCI3,... 

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