10.1021/acs.jnatprod.8b01083.s001 Corey M. Griffith Corey M. Griffith Abigail Feceu Abigail Feceu Cynthia K. Larive Cynthia K. Larive David B. C. Martin David B. C. Martin Synthesis and Structure Reassignment of Malylglutamate, a Recently Discovered Earthworm Metabolite American Chemical Society 2019 sample HMBC Earthworm Metabolite Malylglutamate diastereomer NMR spectra 2019-02-08 20:19:22 Journal contribution https://acs.figshare.com/articles/journal_contribution/Synthesis_and_Structure_Reassignment_of_Malylglutamate_a_Recently_Discovered_Earthworm_Metabolite/7697942 Malylglutamate, a newly identified metabolite in earthworms, was synthesized using a traditional peptide coupling approach for assembling the amide from protected malate and glutamate precursors. The proposed structure (<b>1</b>) and a diastereomer were synthesized, but their NMR spectra did not match the natural sample. Further analysis of the natural sample using HMBC spectroscopy suggested an alternative attachment of the malyl moiety, and β-malylglutamate (<b>2</b>) diastereomers were synthesized, L,L-<b>2</b> and D,D-<b>2</b>. NMR spectra were an excellent match with the natural sample, and chiral-phase chromatography was employed to identify (−)-β-l-malyl-l-glutamate (<b>2</b>) as the isomer native to <i>Eisenia fetida</i>.