Synthesis of a Family of Triarylphosphanes with Fluorous Phase Affinity

The first fluorous biphase hydrogenation catalyst incorporating a perfluoropolyalkylether: [RhCl(PPh2(C6H4C(O)OCH2CF(CF3)(OCF2CF(CF3))nF))3] with n=4–9

“…Characterization of the resulting complex 4, [RhCl(PPh 2 (C 6 H 4 R F )) 3 ] (where R F = C(O)OCH 2 CF(CF 3 )(OCF 2 CF(CF 3 )) n F with n = 4-9), a red oil, was accomplished primarily through 31 triplets at 47.66 ppm ( 1 J PRh = 187.8 Hz, 2 J PP = 35.2 Hz, 1P) was observed. However a doublet appearing at 51.51 ppm (d, 1 J PRh = 189.98 Hz) was suggestive of an equilibrium between 4 and a chloro-bridged dimer as shown in Scheme 3, as has been observed previously [16].…”

“…Following the stirring period, the upper organic layer was decanted. The lower fluorinated phase was washed once with 2 mL of dry degassed toluene and the volatiles from the fluorinated layer were removed in vacuo affording 4 as a red oil (52% yield by 31 …”

“…Fig. 2 provides a sampling of various representative fluorinated phosphine ligands that have been prepared [16,18,24,[26][27][28][29][30][31][32][33][34][35][36].…”

Electrophilic polyfluoroalkylating agents based on sulfonate esters

“…Thus, mesylates and tosylates can be extracted between water and chloroform following by washing with a solution of sodium hydrogen carbonate and brine [12]. For the more reactive sulfonates such as triflates or nonaflates, this work up technique is not recommended, but it has been successfully used for the separation extraction between aqueous and organic system [23,24]. Alternatively, they can be separated by simple filtration through a short column of silica gel and eluted with dichloromethane [12,20,21].…”

“…The preparation of the (perfluoroheptyl)methyl nonaflate utilizes the corresponding fluoride of the sulfonic acid. Thus, (perfluoroalkyl)methyl nonafluorobutanesulfonate, was easily obtained by treating (perfluoroalkyl)methanols with a slight excess of C 4 F 9 SO 2 F in diethylether or dichloromethane in the presence of triethylamine [23,68,69] with high yields (Scheme 5).…”