Mass spectrometric study of the amipurimycin hexopyranosidic sugar moiety

Abstract

Amipurimycin is a natural nucleoside that displays a remarkable activity in vitro and in vivo against Pyricularia oryzae, which is responsible for the rice blast disease. Six important precursors for the synthesis of the Amipurimycin sugar moiety were prepared. In order to obtain structural information a mass spectrometric study of these compounds was performed using liquid secondary ion mass spectrometry (LSIMS) with high-energy collision-induced dissociation (CID) experiments on a four-sector instrument. Elimination of methanol is the preferential fragmentation path for five of the six protonated molecules, indicating that protonation plays an important role in the process, whilst for the other protonated molecule loss of water is the main fragmentation. Examination of the [M + Li] + precursor ion spectra shows that loss of methanol does not occur in three of them, but in the other three gives rise to fairly abundant ions, indicating that in this case methanol elimination implies intramolecular hydrogen transfer, the resulting ion having a very stable structure.