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Polystyrene and polymethacrylate-based resin supported Jacobsen's chiral Mn salen complexes have been prepared. The resins are of defined molecular structure and morphology, and the complexes have been attached primarily in a pendant fashion. The loadings of Mn() are in the range ~0.08-0.35 mmol g Ϫ1 to maximise the likelihood of site-isolation. The polymer-supported complexes have been used as enantioselective catalysts in the epoxidation of 1,2-dihydronaphthalene, indene, 1-phenylcyclohex-1-ene and 1-phenyl-3,4-dihydronaphthalene using m-chloroperbenzoic acid as the oxidant and 4-methylmorpholine N-oxide as the co-oxidant. Though the activities of the polymer catalysts are reduced relative to the soluble homogeneous analogue, the catalysts are sufficiently active to be useful. The corresponding reduction in enantioselectivity is more significant, and is both substrate and polymer resin dependent. However, in the case of 1-phenylcyclohex-1-ene and a macroporous polymethacrylate-based resin the enantioselectivity is equivalent to that of the soluble complex (91-92% ee). This is the first report of a polymersupported analogue of Jacobsen's catalyst being as selective as the homogeneous species. The catalysis data is discussed in detail in the context of the design of the polymer-supported system, and the existing data already available in the literature.Attempts have also been made to recycle the polymer catalysts with and without re-loading of Mn. In fact the level of leaching of Mn is very low, but the catalysts show a very rapid fall off in both activity and selectivity in the first and second cycles. Overall therefore it seems that the intrinsic stability of the chiral Mn() salen complex itself is too low to allow viable recycling, and the development of other more stable supported chiral metal salen complexes for use in other enantioselective reactions seems a better future option.

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Homogeneous linear poly(tartrate ester) ligands provide high chemical yields and enantiomeric excesses in the epoxidation of trans-hex-2-en-1-ol using Ti(OPr i ) 4 -tert-butyl hydroperoxide. Branched poly(tartrate ester) can be use as heterogeneous ligands in the epoxidation of trans-hex-2-en-1-ol using Ti(OPr i ) 4 -tert-butyl hydroperoxide. Removal and recovery of the polymer catalyst is a simple filtration at the end of reactions.

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