The enantioselective total syntheses of himandravine and GB17 were completed through a common biomimetic strategy involving Diels-Alder reactions of unusual double diene containing linear precursors. The double diene precursors, containing or lacking a C12 substituent as required to produce GB17 or himandravine, respectively, were found to undergo Diels-Alder reactions to afford mixtures of regioisomeric cycloadducts that map onto the alternative carbocyclic frameworks of both himandravine and GB17. Computational investigations revealed that these Diels-Alder reactions proceed via transition state structures of similar energy that have a high degree of bispericyclic character and that the low levels of regioselectivity observed in the reactions are a consequence of competing orbital interaction and distortion energies. The combined experimental and computational results provide valuable insights into the biosynthesis of the Galbulimima alkaloids.

Despite the reduction in industrial use of toxic heavy metals, there remain contaminated natural water sources across the world. Herein we present a modular platform for developing selective sensors for toxic metal ions using N-substituted glycine, or peptoid, oligomers coupled to a fluorophore. As a preliminary evaluation of this strategy, structures based on previously identified metal-binding peptoids were synthesized with terminal pyrene moieties. Both derivatives of this initial design demonstrated a turn-off response in the presence of various metal ions. A colorimetric screen was designed to identify a peptoid ligand that chelates Hg(ii). Multiple ligands were identified that were able to deplete Hg(ii) from a solution selectively in the presence of an excess of competing ions. The C-terminal fluoropeptoid derivatives demonstrated similar selectivity to their label-free counterparts. This strategy could be applied to develop sensors for many different metal ions of interest using a variety of fluorophores, leading to a panel of sensors for identifying various water source contaminants.