title: Unidirectional triple hydrogen rearrangement in the radical cations of electron-rich 3-aryl-1-propanols: further evidence and limitation.
abstract: The unidirectional triple-hydrogen (3H) rearrangement of the radical cations of 3-aryl-1-propanols bearing an electron-rich substitutent in the para-position was investigated for the diastereomeric 2-(4-dimethylamino)benzylcyclohexanols and 2-(4-dimethylamino)-benzylcyclopentanols and confirmed to be a highly stereospecific feature. Whereas the standard electron ionization (EI) (70 eV) mass spectra of the trans-isomers exhibit very minor (approximately 2%-3%) albeit stereospecific peaks for the relevant C8H13N*+ ions (m/z 123), the metastable ion [mass-analyzed ion kinetic energy (MIKE)] spectra show these peaks with significant relative intensity (8%-17%). The respective cis-isomers do not undergo the 3H rearrangement, be it under standard or under metastable-ion conditions. The stereospecific 3H rearrangement is suppressed in the radical cations of cis- and trans-3-(4-dimethylamino)phenylcyclohexanol, the mass and MIKE spectra of which are governed by cleavage processes of the cyclohexane ring, which impedes the stereochemical assignment of the isomers by mass spectrometry. A multistep mechanism for the unidirectional 3H rearrangement is discussed in view of the present and previous experimental data.
authors.forename: Dietmar
authors.initials: D
authors.lastname: Kuck
authors.forename: Linda C
authors.initials: LC
authors.lastname: Salameh
authors.forename: Kenneth I
authors.initials: KI
authors.lastname: Onwuka
authors.forename: Matthias C
authors.initials: MC
authors.lastname: Letzel