Synthesis and Configuration Confirmation of the ATHOD Fatty Amino Acid Residue in the Burkholdines.

Abstract

Eight possible diastereomers of the 3-amino-5,6,7-trihydroxy octadecanoic acid (ATHOD) moiety of the burkholdines (Bks) have been synthesized and their configurations assigned. Though the relative configuration of the triol in the ATHOD residue of the Bks was proposed to be anti-anti-anti in the literature, 1H NMR spectra of our synthesized anti-anti-anti ATHOD derivative was inconsistent with that of the isolated ATHOD residue, suggesting that the assignment of the relative configuration of that residue in the literature was incorrect. However, by comparison of the NMR data of our ATHOD derivatives with that of configurationally defined samples of 2-amino-4-pentanol using Kishi's NMR database method, we conclude that the absolute configuration of the ATHOD moiety is (3R,5S,6R,7S). In addition, we revealed that the ATHOD residue present in the occidiofungins A-D has the same configuration as that in all the Bks.