A convenient access to triarylphosphines with fluorous phase affinity

Synthesis of a Family of Triarylphosphanes with Fluorous Phase Affinity

“…19 F NMR (CDCl 3 ): δ ϭ Ϫ126.6 (s, 6 F), Ϫ123.5 (s, 6 F), Ϫ123.2 (s, 6 F), Ϫ122.5 (s, 12 F), Ϫ119.9 (s, 6 F), Ϫ81.2 (t, 3 J F,F ϭ 10 Hz, 9 F). 31 2-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxy 30 mL), the combined organic phases were washed with an saturated aqueous solution of NaCl (2 ϫ 30 mL) and dried over Na 2 SO 4 . Evaporation of the solvent gave a residue that was purified by column chromatography using CH 2 Cl 2 /diethyl ether (1:1) as the eluent to give 0.72 g of the phosphane oxide 6 (yield 42%) as a white solid.…”

“…R f ϭ 0. 31 3 J C,P ϭ 13.0 Hz, C arom ), 124.9 (d, 1 J C,P ϭ 113.2 Hz, C arom ), 133.9 (d, 2 J C,P ϭ 11.3 Hz, C arom ), 161.3 (s, C arom .) 19 F NMR (CDCl 3 ): δ ϭ Ϫ123.6 (s, 6 F), Ϫ123.9 (s, 6 F), Ϫ123.2 (s, 6 F), Ϫ122.4 (s, 18 F), Ϫ114.8 (s, 6 F), Ϫ81.3 (t, 3 J F,F ϭ 9.5 Hz, 9 F).…”

“…[28,29] More recently, a palladiumcatalyzed Heck olefination of haloarylphosphane oxides with perfluoroalkenes, followed by reduction, also afforded perfluoroarylphosphanes in high yields. [30] We have previously published a preliminary communication [31] concerning a convenient access to triarylphosphanes with fluorous-phase affinity, where the aliphatic fluorocarbon chain was attached to the aromatic ring by a hydroxyl group. In this paper we present a full account of this approach and its extension to other phosphanes.…”

Fluorous Organometallic Chemistry

“…In 2011, a series of luminescent iridium(III) biscyclometalated cations [Ir(N-C) 2 (N-N)](PF 6 ) with two C 8 F 17 ponytails were reported, in which the fluorous substituents appeared to impact positively on the photophysical and biological properties [121]. The oxime-based palladacycle (24), formed in a slow reaction of the free oxime with Li 2 PdCl 4 in acetone at reflux, has been shown to be a highly effective pre-catalyst for SuzukiMiyaura, Sonagashira, Stille, Heck and Kumada reactions, either in aqueous solution or organic solvents, that could be recycled and reused up to five times [122,123]. The first metal-pincer ligand complex was reported in 1998.…”

“…More recently, there has been interest in the development of alternative fluorophilic segments based upon smaller perfluorinated groups, e.g. -OC(CF 3 ) 3 [12][13][14][15][16][17][18][19][20][21][22], or perfluoropolyethers [23][24][25][26][27][28][29] that are designed to reduce the potential environmental impact of the degradation products of organic or organometallic species derivatised with long perfluoroalkyl groups [30][31][32][33], but their applications in organometallic systems have been restricted to just a couple of research articles.…”