Hybrid density functional theory study of fragment ions generated during mass spectrometry of 1,3-dioxane derivatives.

It was recently reported that the cis,cis and trans,trans diastereoisomers of four 2(r)-R-2,4(R),6(S)-trimethyl-1,3-dioxane derivatives show distinct electron ionization mass spectra. As a possible explanation for this finding, the authors suggested that the ions generated during the mass spectrometry of these compounds could follow different fragmentation patterns that initiate from different ion conformations. In this report, hybrid density functional theory methods have been used to investigate the conformational preference of three ions involved in the mass spectrometry of some 1,3-dioxane derivatives. We found that there is indeed more than one stable ion conformation for each of the investigated ions. Energy profiles along the torsional coordinates connecting the conformers are presented, and factors influencing the relative stability of ion conformations are discussed.