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4-Dimethylaminopyridine (DMAP) is a highly efficient and important organocatalyst used for a variety of organic reactions,[1] including the acylation [2] and silylation [3] of hindered alcohols, the Baylis–Hillman reaction [4] and the ringopening polymerisation of lactide and other lactones.[5] Heterogeneous versions [6] supported on soluble [7] and crosslinked polymers [8] as well as inorganic nanoparticles [9] have been described. Soluble catalysts and nanoparticles can show high activities but require extra isolation steps for catalyst recycling. On the other hand, catalysts supported on insoluble polymer beads, whilst being simple to recycle, tend to suffer from a drop in activity compared to the homogeneous catalyst. Furthermore, the performance of catalysts supported on gel-type polymer beads is limited by solvent-dependent access to the reactive sites inside the beads.[10] The use of permanently porous (often referred to as macroporous) polymer beads overcomes these solvent limitations,[11] however reactions with these supports can be slow as mass transfer to the active sites on the internal surface of the porous bead occurs by diffusion only. The mass transport limitations of permanently porous beads can be overcome by using emulsion-templated porous polymers (polyHIPEs), which possess very large pores (1–100 μm) permitting mass transfer by convection rather than diffusion.[12] PolyHIPE materials are produced from high internal phase emulsions (HIPEs), where the dispersed phase occupies> 74% of the emulsion volume. PolyHIPEs have been prepared from either oil-in-water (o/w) or water-in-oil (w/o) emulsions and have been …