The first preparation of 2-dimethylaminoimidazole 1a, a structural feature of several marine products was undertaken and its reactivity investigated. The synthesis of natural alkaloids 5 and 12b was achieved by direct coupling of the easily accessible oxidized 2-dimethylaminoimidazoles 7 and 8 with indole-3-carboxaldehyde and indole respectively, demonstrating the usefulness of this approach for other structurally related natural products.