Polystyrene-supported dendrimers

Figure 4.44 Insoluble polystyrene-supported dendrimers bearing proline end groups.

Krishnan GR, Sreekumar K (2008) First example of organocatalysis by polystyrene-supported PAMAM dendrimers highly efficient and reusable catalyst for Knoevenagel condensations. European J Org Chem 281 4763... 

There are reports of numerous examples of dendritic transition metal catalysts incorporating various dendritic backbones functionalized at various locations. Dendritic effects in catalysis include increased or decreased activity, selectivity, and stability. It is clear from the contributions of many research groups that dendrimers are suitable supports for recyclable transition metal catalysts. Separation and/or recycle of the catalysts are possible with these functionalized dendrimers for example, separation results from precipitation of the dendrimer from the product liquid two-phase catalysis allows separation and recycle of the catalyst when the products and catalyst are concentrated in two immiscible liquid phases and immobilization of the dendrimer in an insoluble support (such as crosslinked polystyrene or silica) allows use of a fixed-bed reactor holding the catalyst and excluding it from the product stream. Furthermore, the large size and the globular structure of the dendrimers enable efficient separation by nanofiltration techniques. Nanofiltration can be performed either batch wise or in a continuous-flow membrane reactor (CFMR). 

The combination of an efficient control over the environment of the active sites in a multi-functional catalyst and its immobilization within an insoluble macromolecular support was pioneered by Seebach et al. In their approach, the chiral ligand to be immobilized was placed in the core of a polymerizable dendrimer, followed by copolymerization of the latter with styrene as shown in Scheme 9 [58]. In this way, no further cross-finking agent was necessary, since the dendrimer itself acted as cross-linker. The dendritic branches are thought to act as spacer units, keeping the obstructing polystyrene backbone... 

There have been multiple efforts toward supported catalysts for asymmetric transfer hydrogenation, and the 4 position on the aryl sulfonate group of 26 has proven a convenient site for functionalization. Thus far, this ligand has been supported on dendrimers [181,182], polystyrenes [183], silica gel [184], mesoporous siliceous foam [185], and mesoporous siliceous foam modified with magnetic particles [186]. The resulting modified ligands have been used in combination with ruthenium, rhodium, and iridium to catalyze the asymmetric transfer of imines and, more commonly, ketones. 

Throughout this chapter, the convention of representing a polymer support by a shaded sphere is used when referring to a simple polystyrene backbone. For grafted supports derived from polystyrene, the same shaded sphere is used but the grafted fragment will be shown. For dendrimer-derived supports, a shaded star is used and the ( ) generation of the dendrimer represented by the suffix G . 

In the first approach, prolinamides have been supported on micelleforming species, dendrimers (32a-c), polystyrene (26, 31a-d), poly-vinylidene chloride, phenolic polymers, ionic liquids, silica (28, 29), other inorganic supports (30), ° and polymer-modified small peptides. Supported prolinamide catalysts have also been prepared by acrylic and styrene (27) copolymerisation. 

Dendrimer- and polymer-supported catalysts can be employed in the ATH of sultam precursors [71, 72], including examples where the supporting material has sulfonyl groups and therefore assists reactions in water [73]. The synthesis of an amphiphilic polystyrene-type immobilized TsDPEN ligand and its application in ATH of cyclic sulfonimines has been reported (Fig. 16) [74]. 

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