Precursors for the selective generation of C-2 glyceryl radicals were synthesized, and the chemical behavior of the corresponding radicals was investigated by ESR spectroscopy, product analysis, and kinetic measurements. It was found that cleavage of the beta-C,O bond proceeds rapidly, if a hydroxyl group is present at the radical carbon center. The rate constant for the elimination of a beta-acetoxy group from radical 30 was dependent on the solvent (k(E)=4x10(5) s(-1) in methanol, k(E)=2x10(7) s(-1) in toluene). With these results and ab initio calculations a concerted elimination mechanism is suggested. alpha-Methoxy-substituted C-2 glyceryl radicals 42 and 43 showed heterolytic beta-C,O bond cleavage under formation of radical cations. With ester-substituted radicals 24 and 35 no elimination could be observed. To demonstrate the biological significance of these findings, C-2 lysolecithin radical 53 was generated, which led to fast beta-elimination.