Effects of stereoisomerism on the electron impact fragmentation of some compounds with an eburnane skeleton1

The mass spectra of five sets of stereoisomers possessing an eburnane basic skeleton (vincamine, vincaminic acid ethyl ester, deoxyvincamine, deoxyvincaminic acid ethyl ester, apovincaminic acid ethyl ester and all their possible epimers) have been compared. All of the epimers, among them the 3H-β isomers, not studied formerly, have characteristically different electron impact spectra. For vincamine and its epimers similar differences were also found in the argon charge exchange ionization, mass-analysed ion kinetic energy and collisionally activated mass-analysed ion kinetic energy spectra. The main effects of stereoisomers on the abundance ratios clearly indicated the occurrence of some highly stereospecific or stereoselective decomposition processes. Conclusions concerning the mechanism of these reactions, based on the normal and metastable ion spectra as well as on some energetic data for the epimers, have also been drawn. For several fragment ions the observed unexpected abundance differences seem to be rationalized in terms of the competing effects of other decomposition processes of higher stereoselectivity.