Triphenylphosphine, perfluorinated

Betzemeier et al. (1998) have used f-BuOOH, in the presence of a Pd(II) catalyst bearing perfluorinated ligands using a biphasic system of benzene and bromo perfluoro octane to convert a variety of olefins, such as styrene, p-substituted styrenes, vinyl naphthalene, 1-decene etc. to the corresponding ketone via a Wacker type process. Xia and Fell (1997) have used the Li salt of triphenylphosphine monosulphonic acid, which can be solubilized with methanol. A hydroformylation reaction is conducted and catalyst recovery is facilitated by removal of methanol when filtration or extraction with water can be practised. The aqueous solution can be evaporated and the solid salt can be dissolved in methanol and recycled. 

The perfluorinated cyclopropenes (292, X = C(CF3)NH) may be prepared from (293) by 1,3-dipolar addition of diazomethane followed by desulphurisation with, triphenylphosphine to produce, (294), and then thermolysis. Addition of (292, X = C(CF3)0) to 2,3-dimethylbutadiene occurs predominantly in an endo-manner, the intermediate undergoing an intramolecular ene-reaction to produce (295). In the same way reaction with pyrrole leads to (296), in this case presumably by an intramolecular nucleophilic attack in the initially formed endo-adduct 237). 

One of the main drawbacks of the Wittig reaction is the formation of unwanted triphenylphosphine oxide. A new route, which makes use of polymer-supported triphenylphosphine and microwave dielectric heating has been developed (Scheme 13), which yields the required alkene without the triphenylphosphine oxide. An alternative strategy for separation of the product alkene from unwanted phosphine oxide by-product is to carry out the Wittig reaction in a fluorous solvent using a perfluorinated ylide such as (45). One drawback of this... 

Scheme 4.7-6 Rhodium-catalyzed hydroformylation in SCCO2 [11]. The notation used here and in the text defines perfluorinated alkyl substituents of general formula (CH2)y(CF2)zF with the x giving the substitution position relative to phosphorus [22]. TPP and TPOP are used as acronyms for triphenylphosphine and triphenylphosphite, respectively. 1) pical results are listed in Table 4.7-3 and represented in Figure 4.7-5.

Microwave-mediated fluorous reaction conditions for palladium-catalyzed aminocarbonylations have been discussed in a more recent report [101]. A set of aryl halides was reacted with carbonyl hydrazides and molybdenum hexacarbonyl [Mo(CO)e] as source of carbon monoxide, with fluorous triphenylphosphine (F-TPP) as ligand and the perfluorocarbon liquid FC-84 as perfluorinated solvent (Scheme 16.67). 

The RAPTA structure has also been modified with a triphenylphosphine ligand (Fig. 13.14) to give a complex with improved cytotoxicity, cellular uptake and higher affinity towards DNA [40, 41]. Various other phosphines co-ligands have also been evaluated, notably phosphine moieties with perfluorinated alkane chains that were found to endow the compounds with thermosensitive properties (Fig. 13.14) [42]. Thermotherapy is a treatment in which a heat source is applied... 

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