Small molecules have been used to explore many facets of biology for over a century. However, research in biology is not routinely performed using this approach, in the way that it is with biochemical, genetic, and increasingly, genomic approaches. Several problems limit the use of the former approach. Arguably, the primary one is the lack of routine access to structurally complex and diverse small molecules that can be used to modulate biological systems.[1] Diversityoriented organic synthesis, especially when coupled with an economical and efficient technology platform, offers the means to change this situation, as it aims to synthesize complex and diverse small molecules efficiently.[2] Diversityoriented synthesis is central to chemical genetics, which aims to explore biology with small molecules in a systematic way.[3] Although enantioselective catalysis is often used in targetoriented synthesis, it is still relatively underexplored in diversity-oriented synthesis.[4, 5] We have been interested in reactions catalyzed by bis(oxazoline)metal Lewis acid complexes because of their high efficiency, selectivity, and broad substrate tolerance.[6] We chose to concentrate on inverse electron demand heterocycloadditions of vinyl ethers and b,gunsaturated ketoesters (Scheme 1).[7, 8] An account of related cycloadditions on solid support has been described;[9] however, the reported reactions were performed in the presence of achiral catalysts and with the heterodiene bound to the PS solid support through the ester. We initially investigated this mode of cycloaddition and found it to be highly selective when the enantiomerically pure catalysts (S)or (R)-1 were used.[5, 8] However, in the interest of effectively functionalizing the cycloadduct, we found an alternative mode using support-bound vinyl ethers, linked to a macrobead through either carbon or oxygen, to be more effective.