Chiral recognition between lactic acid derivatives and an aromatic alcohol in a supersonic expansion: electronic and vibrational spectroscopy

Abstract

Jet-cooled diastereoisomeric complexes formed between a chiral probe, (+/-)-2-naphthyl-1-ethanol, and chiral lactic acid derivatives have been characterised by laser-induced fluorescence and IR fluorescence-dip spectroscopy. Complexes with non chiral alpha-hydroxyesters and chiral beta-hydroxyesters have also been studied for the sake of comparison. DFT calculations have been performed to assist in the analysis of the vibrational spectra and the determination of the structures. The observed 1 : 1 complexes correspond to the addition of the hydroxy group of the chromophore on the oxygen atom of the hydroxy in alpha-position relative to the ester function. Moreover, (+/-)-methyl lactate and (+/-)-ethyl lactate complexes with (+/-)-2-naphthyl-1-ethanol show an enantioselectivity in the size of the formed adducts: while fluorescent 1 : 1 complexes are the most abundant species observed when mixing (S)-2-naphthyl-1-ethanol with (R)-methyl or ethyl lactate, they are absent in the case of the SS mixture, which only shows 1 : 2 adducts. This property has been related to steric hindrance brought by the methyl group on the hydroxy-bearing carbon atom.