Fluorination of phosphorus(+3) derivatives by xenon difluoride

Chemistry of xenon derivatives. Synthesis and chemical properties

“…353 The fluorination of four-coordinated phosphorus derivatives containing P7H bonds results in fluorides. 441 The oxidation of organic derivatives of phosphorus(III) containing P7N, P7S or P7O bonds is complicated due to easy elimination of PF 5 which is accompanied by the formation of compounds containing a P = X fragment (X = N, O, S). For example, the fluorination of bis(difluorophosphino)methylamine ( 296) by XeF 2 gives difluorophosphino(tetrafluorophosphoranyl)methylamine (297), which undergoes dimerisation to give compound 298.…”

“…442 Silyl esters and silyl-substituted amides of trivalent phosphorus acids are oxidised by XeF 2 to dialkylphosphofluoridates or dialkyl fluorophosphazenes, respectively. 441 An unusual reaction takes place on the interaction of isobutyl phosphodifluoridite with catalytic amounts of XeF 2 . In this case, the tert-butylphosphonic difluoride was isolated as the main product in 50% yield.…”

“…In this case, the tert-butylphosphonic difluoride was isolated as the main product in 50% yield. 441,443 Presumably, 441 this reaction occurs through the formation of alkoxytetraphenylphosphorane, which disproportionates with the formation of the isobutyl cation. 443 The latter undergoes isomerisation and reacts with the original phosphite to afford the final product.…”

TFAA/DMSO‐Promoted Fluorination of P(O)−H and P(O)−OH Compounds: Compatible Access to Fluorophosphonates and Phosphonofluoridates

“…For P(O)À H compounds, the nucleophilic and electrophilic fluorination system dominate this field (Scheme 1a, path A), [7,8] using reagents such as trichloroacetonitrile (TCA)/KF, trichloroisocyanuric acid (TCICA)/KF, TolIF 2 , XeF 2 , selectfluor, etc. With regard to P(O)À OH compounds, some deoxygenative fluorination systems have been developed (Scheme 1a, path B), [9] with (diethylamino)sulfur trifluoride (DAST), SF 4 , SOF 2 and 2,4-dinitrofluorobenzene (DNFB) being the most commonly used fluorinating reagents.…”

Direct, oxidative halogenation of diaryl- or dialkylphosphine oxides with (dihaloiodo)arenes

“…For example, in reactions with TCICA-KF, 11 trichloroacetonitrile-KF 12 or CuCl 2 -CsF, 13 the initially-formed chlorides are intercepted by the fluoride. Electrophilic fluorination of a phosphine oxide is achieved with reagents such as XeF 2 , 14 Selectfluor ®15 or DDQ/CuBr 2 /NaF. 16 Drawbacks of these methods include harsh reaction conditions, the need for excess reagent, or use of reagents that are corrosive, toxic, costly or moisture sensitive, therefore the continued development of synthetic strategies remains important.…”