Stereospecific fragmentation processes in cycloalkane/cycloalkene-fused isomers of saturated pyrrolo[2,1- b][1,3]oxazin-6-one derivatives

Abstract

Electron ionization-induced fragmentations were studied in a set of saturated pyrrolo[2,1- b][1,3]oxazin-6-one derivatives fused to either cycloalkane or cycloalkene rings, including seven pairs of cis/trans and endo/exo annelation isomers. Fragmentation patterns were confirmed by accurate mass measurements and metastable ion spectra. A number of striking differences were observed between the mass spectra of cyclohexene-fused isomers due to highly stereospecific retro-Diels-Alder (RDA) fragmentation of their M +· ions. The observed 90% stereospecificity is abnormally high in the light of the recent classification (A. Mandelbaum, 1994) of stereospecific RDA fragmentations according to the degree of substitution of the cyclohexene ring being cleaved. In the absence of RDA processes, the differences between the mass spectra of cyclohexane-fused isomers originated from heterocyclic fragmentations. The assumed mechanistic interpretation of the observed differences, e.g., in the formation of [M − C 3H 5O] + ions, was consistent with the condensed-state conformations of these isomers determined previously by NMR and X-ray diffraction studies. Because of rapid RDA decompositions of their rather unstable M +· ions, the spectra of the di endo/di exo norbornene-fused isomers were virtually identical.