Stereoselective polysiloxanes

Asymmetric Diels-Alder reactions have also been achieved in the presence of poly(ethylene glycol)-supported chiral imidazohdin-4-one [113] and copper-loaded silica-grafted bis(oxazolines) [114]. Polymer-bound, camphor-based polysiloxane-fixed metal 1,3-diketonates (chirasil-metals) (37) have proven to catalyze the hetero Diels-Alder reaction of benzaldehyde and Danishefsky s diene. Best catalysts were obtained when oxovanadium(lV) and europium(III) where employed as coordinating metals. Despite excellent chemical yields the resulting pyran-4-ones were reported to be formed with only moderate stereoselectivity (Scheme 4.22). The polymeric catalysts are soluble in hexane and could be precipitated by addition of methanol. Interestingly, the polymeric oxovanadium(III)-catalysts invoke opposite enantioselectivities compared with their monomeric counterparts [115]. 

Amino-fimctionalized polysiloxanes (Deloxan ) with tertiary amines incorporated in the silica matrix, show a similiar behaviour. The tertiary amine can be omitted, but the stereoselectivity of this catalyst was lower than that of the conventional catalysts (see Table 3). 

The application of polymer-supported catalysts has now been extended to the synthesis of complexes between transition metal derivatives and structurally ordered macromolecular ligands to give catalytic systems exhibiting high activity and stereoselectivity. Polystyrene and polymethacrylate resin and polystyrene-divinylbenzene-polystyrene-polybutadiene block copolymers, as well as vinyl-functionalized polysiloxanes grafted onto silica, are very suitable polymers for heterogenization of mostly Pt and Rh complexes. Moreover, polyamides exhibit much higher thermal stability than conventional polystyrene supports (114). 

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