Phosphorus(III) ligands in fluorous biphase catalysis

Addition of Perfluoroalkylethane Thiols to Bis(Propargyl) Polyoxyethylene Ethers: Synthesis of Tetrakis-(F-Alkylethanethio) Polyoxyethylene Ethers

“…The separation of the two asymmetric centers of the molecule by the polyoxyethylene ether chain renders the interaction between these two sites negligible in a manner that they can be considered as two independent asymmetric centres and NMR spectroscopy is therefore expected to be unable to distinguish between the two diastereoisomers. 17 The coexistence of four F-alkylated chains and four sulfur atoms linked to a modulable polyoxyethylene chain may be the origin of the interesting applications associating the well-known proprieties of highly fluorinated compounds 18,19 to those related to the existence of sulfur atoms.…”

“…14 In view of these results, we present herein the synthesis of new tetrakis-(F-alkylethanethio) polyoxyethylene ether derivatives 2a-d by radical addition of perfluoroalkylethane thiols to bis(propargyl) polyoxyethylene ethers 1. All compounds were fully characterized by their spectroscopic 1 H, 13 C, 19 F NMR, and HRMS data. These new tetrakis-adducts containing two terminal F-alkylethanethio groups bridged by a polyoxyethylene chain may be useful as models for further studies.…”

Electrophilic polyfluoroalkylating agents based on sulfonate esters

“…In other applications, (perfluoroheptyl)methyl nonaflate was used for alkylation of tris(4-hydroxyphenyl)phosphine (74) [94], tris(4-hydroxyphenyl)phosphine oxide (75) [95] and tris(3,5-dihydroxyphenyl)phospine oxide (76) [96]. The reactions were carried out in dimethylformamide as a solvent with potassium or cesium carbonate and afforded the desired polyfluorinated ligands 77-79 in 32-75% yields (Scheme 27).…”

(R)-2,2′-Bis(diphenylphosphino)-6,6′-bis(tridecafluoro-n-hexyl)-1,1′-binaphthyl

“…More recently, we turned our attention to asymmetric catalysis, including the synthesis of (R)-2,2 0 -bis(diphenylphosphino)-6,6 0 -bis(tridecafluoro-n-hexyl)-1,1 0 -binaphthyl and (R)-2,2 0 -bis(diphenylphosphino)-6,6 0 -bis(1H,1H,2H,2H-tridecafluorooctyl)-1,1 0binaphthyl, and their application in ruthenium-catalysed hydrogenation in methanol (Birdsall et al, 2001) and dichloromethane with ligand recycling using fluorous silica gel (Hope et al, 2004). Although we have previously structurally characterized perfluoroalkylated triphenylphosphine oxides (Bhattacharyya et al, 2000;Croxtall et al, 2002), there have been no previous single-crystal structure determinations of phosphine ligands with fluorous tails. We present here the crystal structure of the title such ligand, (I).…”