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Lariat ethers in the chiral recognition of amino acid esters:electrospray ionization mass spectrometry investigation

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Abstract

The ability of the crown ethers (1–4), containing the ortho- or para- methoxyphenoxy-methyl substituents in their structure, to chiral recognition in reference to amino acid esters has been investigated by electrospray ionization mass spectrometry (ESI-MS). The method allows registering the diastereomeric complexes between the studied crowns as hosts and the protonated alanine, phenylglycine and phenylalanine methyl esters as guests in the gas phase. ESI-MS experiments using isotopically labeled guests provide robust and reproducible results, indicating a moderate degree of chiral discrimination in the series of the studied crown ethers. ESI-MS experiments using achiral amine as a reference yielded the results comparable with the previous method. It has been found that (S)-enantiomers of the crowns bind predominately (S)-enantiomers of the amino acid esters, and vice-versa. It has been shown that the chiral ortho-substituted crown (S)-1 demonstrates the more pronounced values for chiral discrimination as compared with the para-substituted crown (S)-2. This fact indicates the interrelationship between the chiral recognition and the lariat nature of crown 1. Increasing the size of the cavity and the presence of a flat aromatic moiety in crowns 3 and 4 strengthens their complexing ability, simultaneously weakening the enantioselectivity of the complexation.

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Authors and Affiliations

  1. A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Arbuzov St. 8, Kazan, 420088, Russia

    Zemfira A. Bredikhina, Dilyara R. Sharafutdinova, Olga B. Bazanova, Vasily M. Babaev, Robert R. Fayzullin, Ildar Kh. Rizvanov & Alexander A. Bredikhin

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  1. Zemfira A. Bredikhina
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  2. Dilyara R. Sharafutdinova
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  3. Olga B. Bazanova
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  4. Vasily M. Babaev
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  5. Robert R. Fayzullin
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  6. Ildar Kh. Rizvanov
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  7. Alexander A. Bredikhin
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Correspondence to Alexander A. Bredikhin.

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Bredikhina, Z.A., Sharafutdinova, D.R., Bazanova, O.B. et al. Lariat ethers in the chiral recognition of amino acid esters:electrospray ionization mass spectrometry investigation. J Incl Phenom Macrocycl Chem 80, 417–426 (2014). https://doi.org/10.1007/s10847-014-0430-6

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  • DOI: https://doi.org/10.1007/s10847-014-0430-6

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