Chiral discrimination of β-3-homo-amino acids using the kinetic method

Abstract

Chiral discrimination of seven enantiomeric pairs of β-3-homo-amino acids was studied by using the kinetic method and trimeric metal-bound complexes, with natural and unnatural α-amino acids as chiral reference compounds and divalent metal ions (Cu(2+) and Ni(2+) ) as the center ions. The β-3-homo-amino acids were selected for this study because, first of all, chiral discrimination of β-amino acids has not been extensively studied by mass spectrometry. Moreover, these β-3-homo-amino acids studied have different aromatic side chains. Thus, the emphasis was to study the effect of the side chain (electron density of the phenyl ring, as well as the difference between phenyl and benzyl side chains) for the chiral discrimination. The results showed that by the proper choice of a metal ion and a chiral reference compound, all seven enantiomeric pairs of β-3-homo-amino acids could be differentiated. Moreover, it was noted that the β-3-homo-amino acids with benzyl side chains provided higher enantioselectivity than the corresponding phenyl ones. However, increasing or decreasing the electron density of the aromatic ring by different substituents in both the phenyl and benzyl side chains had practically no role for chiral discrimination of β-3-homo-amino acids studied. When copper was used as the central metal, the phenyl side chain containing reference molecules (S)-2-amino-2-phenylacetic acid (L-Phg) and (S)-2-amino-2-(4-hydroxyphenyl)-acetic acid (L-4'-OHPhg) gave rise to an additional copper-reduced dimeric fragment ion, [Cu(I) (ref)(A)](+) . The inclusion of this ion improved noticeably the enantioselectivity values obtained.