Aromatic aldehyde-catalyzed gas-phase decarboxylation of amino acid anion via imine intermediate: An experimental and theoretical study

Abstract

It is generally appreciated that carbonyl compound can promote the decarboxylation of the amino acid. In this paper, we have performed the experimental and theoretical investigation into the gas-phase decarboxylation of the amino acid anion catalyzed by the aromatic aldehyde via the imine intermediate on the basis of the tandem mass spectrometry (MS/MS) technique and density functional theory (DFT) calculation. The results show that the aromatic aldehyde can achieve a remarkable catalytic effect. Moreover, the catalytic mechanism varies according to the type of amino acid: (i) The decarboxylation of α-amino acid anion is determined by the direct dissociation of the CC bond adjacent to the carboxylate, for the resulting carbanion can be well stabilized by the conjugation between α-carbon, CN bond and benzene ring. (ii) The decarboxylation of non-α-amino acid anion proceeds via a SN2-like transition state, in which the dissociation of the CC bond adjacent to the carboxylate and attacking of the resulting carbanion to the CN bond or benzene ring take place at the same time. Specifically, for β-alanine, the resulting carbanion preferentially attacks the benzene ring leading to the benzene anion, because attacking the CN bond in the decarboxylation can produce the unstable three or four-membered ring anion. For the other non-α-amino acid anion, the CN bond preferentially participates in the decarboxylation, which leads to the pediocratic nitrogen anion.