Unusual pharmacophores. Chemical reactions underlie the biological mechanisms of many small molecules. Insight into chemical reactivity can therefore inform biology. Our laboratory has invented methods to easily access several classes of secondary metabolites that contain unique pharmacophores and whose covalent cellular reactivity is not understood. We are working to understand 1) the Nuphar dimers, which contain a covalently-reactive thiaspirane pharmacophore; 2. the asmarine alkaloids, whose N-hydroxydiazepine purine may bind metals, react covalently or oxidize a biomolecule; and 3. the isocyanoterpenes (ICTs), antimalarial marine metabolites whose isonitrile function may affect diverse bioinorganic processes. To study this latter class, we invented a general stereochemical inversion of tertiary alcohols.