Polymer bound phosphine catalysts

N.L. Holy, Polymer bound phosphine catalysts. Chapter 14 in L.H. Pignolet, Ed., Homogeneous Catalysts with Metal Phosphine Complexes, Plenum, New York, 1983. 

A number of modified reaction conditions have been developed. One involves addition of silver salts, which activate the halide toward displacement.94 Use of sodium bicarbonate or sodium carbonate in the presence of a phase-transfer catalyst permits especially mild conditions to be used for many systems.95 Tetraalkylammonium salts often accelerate reaction.96 Solid-phase catalysts in which the palladium is complexed by polymer-bound phosphine groups have also been developed.97 Aryl chlorides are not very reactive under normal Heck reaction conditions, but reaction can be achieved by inclusion of triphenylphosphonium salts with Pd(OAc)2 or PdCl2 as the catalyst.98... 

The homogeneous chiral phosphine/DPEN-Ru catalyst can be immobilized by use of polymer-bound phosphines such as polystyrene-anchored BINAP (APB-BINAP) [57, 98], Poly-Nap [99], and poly(BINOL-BINAP) [100], poly(BINAP) [101]. These complexes hydrogenate T-acetonaphthone and acetophenone with S/C of 1000-10 000 under 8 10 atm H2 to give the corresponding secondary alcohols in 84-98% e.e. The recovered complexes are repeatedly used without significant loss of reactivity and enantioselectivity. Immobilization allows the easy separation of catalyst from reaction mixture, recovery, and reuse. These advantages attract much attention in combinatorial synthesis. 

The reaction of an alcohol and a carboxylate anion with diethyl azodicarbox-ylate EtOOCN=NCOOEt and PhsP is called the Mitsunobu esterification reac-tion. This reaction can also be considered as an 8 2. Other Mitsunobu catalysts are available, " and a polymer-bound phosphine has been used. A renewable phosphine ligand has been developed. Note that other functional groups, including azides and thiocyanates can be generated from alcohols using Mitsunobu conditions. 

For ultrafiltration as a unit operation for the separation of polymer-bound soluble catalysts in particular, the recovery process for a rhodium catalyst from the hydroformylation of dicyclopentadiene is an illustrative example (for another detailed example, see Section 7.5) [26, 27]. Toluene can be used as a solvent with the polyaramide membrane employed. TPPTS or also a sulfonated bidentate phosphine with large ammonium counterions, are used as ligands. For efficient recovery, molecular weights of the catalyst of more than 3000 g mofi were required on the membrane used. Separation is performed in two steps [28]. A pilot plant was run successfully over an extended period of time of three months. 

Generally, the activities of polymer-bound palladium catalysts are less than those of unsupported ones, but here too there are exceptions. Kaneda et al reported that PdCl2, on phosphinated polystyrene was more active than the homogeneous situation.Rates were very solvent dependent— hydrogenation of styrene was slow in dimethyl sulfoxide optimum activity was obtained in solvents of moderate coordinating ability (see Table 6). 

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