Contribution of Solvents to Geometrical Preference in the Z / E Equilibrium of N -Phenylthioacetamide

We studied the / preference of -phenylthioacetamide (thioacetanilide) derivatives in various solvents by means of H NMR spectroscopy, as well as molecular dynamics (MD) and other computational analyses. Our experimental results indicate that the / isomer preference of secondary (NH)thioamides of -ph...

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Veröffentlicht in:Journal of organic chemistry 2022-02, Vol.87 (3), p.1641-1660
Hauptverfasser: Song, Shuyi, Hyodo, Tadashi, Ikeda, Hirotaka, Vu, Kim Anh L, Tang, Yulan, Chan, Erika S, Otani, Yuko, Inagaki, Satoshi, Yamaguchi, Kentaro, Ohwada, Tomohiko
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container_end_page 1660
container_issue 3
container_start_page 1641
container_title Journal of organic chemistry
container_volume 87
creator Song, Shuyi
Hyodo, Tadashi
Ikeda, Hirotaka
Vu, Kim Anh L
Tang, Yulan
Chan, Erika S
Otani, Yuko
Inagaki, Satoshi
Yamaguchi, Kentaro
Ohwada, Tomohiko
description We studied the / preference of -phenylthioacetamide (thioacetanilide) derivatives in various solvents by means of H NMR spectroscopy, as well as molecular dynamics (MD) and other computational analyses. Our experimental results indicate that the / isomer preference of secondary (NH)thioamides of -phenylthioacetamides shows substantial solvent dependency, whereas the corresponding amides do not show solvent dependency of the / isomer ratios. Detailed study of the solvent effects based on molecular dynamics simulations revealed that there are two main modes of hydrogen (H)-bond formation between solvent and (NH)thioacetamide, which influence the / isomer preference of (NH)thioamides. DFT calculations of NH-thioamide in the presence of one or two explicit solvent molecules in the continuum solvent model can effectively mimic the solvation by multiple solvent molecules surrounding the thioamide in MD simulations and shed light on the precise nature of the interactions between thioamide and solvent. Orbital interaction analysis showed that, counterintuitively, the / preference of NH-thioacetamides is mainly determined by steric repulsion, while that of sterically congested -methylthioacetamides is mainly determined by thioamide conjugation.
doi_str_mv 10.1021/acs.joc.1c00801
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subjects Hydrogen Bonding
Magnetic Resonance Spectroscopy
Molecular Dynamics Simulation
Solvents - chemistry
Thioamides - chemistry
title Contribution of Solvents to Geometrical Preference in the Z / E Equilibrium of N -Phenylthioacetamide
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