Barrier to rotation around the Csp2-Csp2 bond of the ketoaldehyde enol ether 
meC(O)CH=CH-OEt as determined by13C NMR and ab initio calculations

Siebert, Hans-Christian; Tajkhorshid, Emad; Dabrowski, Janusz

doi:10.1021/jp004476g

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Barrier to rotation around the C_sp²-C_sp² bond of the ketoaldehyde enol ether meC(O)CH=CH-OEt as determined by ¹³C NMR and ab initio calculations

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Dabrowski, Janusz
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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http://dx.doi.org/10.1021/jp004476g
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Siebert, H.-C., Tajkhorshid, E., & Dabrowski, J. (2001). Barrier to rotation around the C_sp²-C_sp² bond of the ketoaldehyde enol ether meC(O)CH=CH-OEt as determined by ¹³C NMR and ab initio calculations. The Journal of Physical Chemistry A, 105(37), 8488-8494. doi:10.1021/jp004476g.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0029-22AC-F

Abstract

NMR measurements and ab initio calculations were applied to determine the barriers to rotation around formally single bonds of the title methyl-β-ethoxyvinyl ketone, i.e., the vinylogue of the ethyl ester of acetic acid. For comparison, ab initio calculations were performed for α,β-unsaturated, β-N, and β-S substituted ketones. The relative height of the rotational barriers for Csp2−Csp2 and Csp2−X bonds of the MeC(O)−CHCH−X−alkyl(s) analogues was found to be reverse for X = N(alkyl)2 vs X = O-alkyl or X = S-alkyl. This finding is discussed in terms of differences in the electron density distribution in these molecules, resulting from differences in electron-donating properties of the heteroatoms N, O, and S.