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Hemiaminal route for the formation of interstellar glycine: a computational study

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Abstract

Calculations related to two simple two-step paths (path-I: \( {\mathrm{H}}_2\mathrm{C}=\mathrm{O}+\mathrm{N}{\mathrm{H}}_3\to \upalpha -\mathrm{hydroxy}\ \mathrm{amine}\ \overset{+\mathrm{CO}}{\to }\ \mathrm{glycine}, \) path-II: \( {\mathrm{H}}_2\mathrm{C}=\mathrm{NH}+{\mathrm{H}}_2\mathrm{O}\to \upalpha -\mathrm{hydroxy}\ \mathrm{amine}\ \overset{+\mathrm{CO}}{\to }\ \mathrm{glycine} \)) for the formation of glycine have been discussed. Calculations show that at interstellar conditions these two paths are feasible only in hot cores, not in the cold interstellar clouds (cold core formation is possible only if CH2 = NH, H2O (excess) and CO of path-II, react in a concerted manner). For the laboratory synthesis of glycine, the possibility suggested is via path-I and the reaction being carried out as controlled temperature one-pot synthesis. This study can also be extended to other α-amino acids and possibly enantiomeric excess can be expected. We think this work will not only be able to enrich our future understanding about the formation of amino acids in interstellar medium but also be able to suggest alternative paths for laboratory synthesis of amino acids using either Strecker’s or Miller’s ingredients.

Using computational calculations, two different reaction paths which go through a hemiaminal (α-hydroxyamine) intermediate have been proposed. It has been proposed that the reaction \( {\mathrm{H}}_2\mathrm{C}=\mathrm{O}+\mathrm{N}{\mathrm{H}}_3\to \upalpha -\mathrm{hydroxyamine}\ \overset{+\mathrm{CO}}{\to }\ \mathrm{glycine}, \) is a thermodynamically favorable reaction path in the laboratory conditions, if carried out as a controlled temperature one-pot synthesis. On the hand, it has been argued that the reaction\( {\mathrm{H}}_2\mathrm{C}=\mathrm{NH}+{\mathrm{H}}_2\mathrm{O}\to \upalpha -\mathrm{hydroxy}\ \mathrm{amine}\ \overset{+\mathrm{CO}}{\to }\ \mathrm{glycine} \) is a feasible reaction path in the interstellar conditions, if it proceeds not via the hemiaminal route, rather in a concerted reaction path.

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Acknowledgments

The authors like to thank University of Johannesburg for support. ZPN and PB carried out this work while doing their PhD works at University of Johannesburg.

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  1. Department of Chemical Sciences (APK Campus), University of Johannesburg, PO Box 524, Auckland Park, Johannesburg, 2006, South Africa

    Zanele P. Nhlabatsi, Priya Bhasi & Sanyasi Sitha

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  1. Zanele P. Nhlabatsi
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Correspondence to Sanyasi Sitha.

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Energetics data related to the potential energy surfaces for the reactions 1–3, calculated using various methods and basis sets (discussed in the computational section) are tabulated in Table S1 and S2. Also provided with are the optimized Cartesian coordinates of all the stationary points.

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Nhlabatsi, Z.P., Bhasi, P. & Sitha, S. Hemiaminal route for the formation of interstellar glycine: a computational study. J Mol Model 25, 335 (2019). https://doi.org/10.1007/s00894-019-4224-z

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