CC BY 4.0 · Synlett 2022; 33(20): 2004-2008
DOI: 10.1055/s-0042-1751385
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Dispersion Effects

London Dispersion-Assisted Low-Temperature Gas Phase Synthesis of Hydrogen Bond-Inserted Complexes

Manuel Lange 
,
Elisabeth Sennert 
,
Martin A. Suhm  ∗
This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation)-271107160/SPP1807 (ML, dispersion effects), 389479699/RTG2455 (ES, halogenation effects, benchmarking of reaction barriers and hydrogen bond energies) and 405832858 (computer cluster).
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Erratum: London Dispersion-Assisted Low-Temperature Gas Phase Synthesis of Hydrogen Bond-Inserted ComplexesSynlett 2023; 34(07): 873-874
DOI: 10.1055/s-0042-1752671

Abstract

Supersonic expansions of organic molecules in helium carrier gas mixtures are used to synthesize model (pre)reactive complexes at low temperature. Whether or not barriers for hydrogen bond rearrangements can be overcome in this collisional process is not well understood. Using the example of alcohols inserting into intramolecular hydrogen bonds of α-hydroxy esters, we explore whether dispersion energy donors can assist the process in a systematic way. Bromo, iodo, and tert-butyl substitution of benzyl alcohol in the para-position is used to show that the insertion process into methyl glycolate is controllable, whereas it is largely avoided for the chiral methyl lactate homologue. Methyl lactate appears to steer the transient chirality of benzyl alcohol derivatives in a uniform direction relative to the lactate handedness for the OH∙∙∙O=C insertion product, as well as for the competing attachment to the hydroxy group of the ester. A simple rule based on the total binding energy in relation to the rearrangement barrier is tentatively proposed to estimate whether the insertion is feasible or not in such molecular complexes during expansion.

Key words

spectroscopy - chirality induction - gas phase reaction - hydrogen bond topology - halogenation - α-hydroxy esters

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0042-1751385.
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Publication History

Received: 02 September 2022

Accepted after revision: 20 October 2022

Article published online:
23 November 2022

© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commercial purposes or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by/4.0/)

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