Synthesis of Tri- and Tetracoordinate Phosphorus Compounds Containing a PCF3 Group by Nucleophilic Trifluoromethylation of the Corresponding PF Compounds

Synthesis of 1-[bis(trifluoromethyl)phosphine]-1’-oxazolinylferrocene ligands and their application in regio- and enantioselective Pd-catalyzed allylic alkylation of monosubstituted allyl substrates

“…Eventually, lithium–bromide exchange of 3 with n -BuLi at −78 °C, followed by quenching with P(OPh) 3 , provided the phosphonite intermediates which were used without further purification. Subsequently, trifluoromethylation provided the ligands L1a–d in moderate yields, upon treatment with Ruppert’s reagent (TMSCF 3 ) and CsF [ 42 – 45 ]. Notably, ligands L1a–d are moisture and air-stable, and their NMR spectra show no change even after being stored over six months under ambient atmosphere.…”

Electrophilic Trifluoromethylation of Primary Phosphines: Synthesis of a P-Bis(trifluoromethyl) Derivative of BINAP

“…The reaction mixture was stirred at this temperature for 1 h before it was warmed to rt over the course of 3 h. The brown solution was concentrated, and the residue was subjected to FC (silica gel 60, pentane f pentane/Et 2 O, 1:1) to give the title compound as a clear, colorless, volatile oil (109 mg, 0.37 mmol, 74%). 1 7). A solution of (R)-1,1 0 -binaphthyl-2,2 0 -diyl bis(trifluoromethanesulfonate) (6, 10.0 g, 18.2 mmol) in DMSO (80 mL) in a Schlenk flask was degassed by evacuating the system and filling with argon (5Â).…”

Copper-Catalyzed Aerobic Oxidative Trifluoromethylation of H-Phospho­nates Using Trimethyl(trifluoromethyl)silane

“…[10][11][12] In 1997, Burton reported a photochemically induced radical reaction of tetraethyl diphosphite [(EtO) 2 POP(OEt) 2 ] and trifluoroiodomethane in the presence of di-tert-butyl peroxide providing diethyl trifluoromethylphosphonate in moderate yield. 11 Later, synthesis of CF 3 -phosphonates via nucleophilic trifluoromethylation of fluorophosphines followed by oxidation or direct nucleophilic trifluoromethylation of P-fluorophosphonates was reported, 12 however, the starting materials are not common and are also not commercially available. Alternatively, Yagupolskii has shown that CF 3 -phosphonates can be prepared from readily available H-phosphonates using diaryltrifluoromethylsulfonium salts as the electrophilic trifluoromethylating reagent.…”