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Storch G, Spallek MJ, Rominger F, et al. Tautomerization-mediated molecular switching between six- and seven-membered rings stabilized by hydrogen bonding. Chemistry. 2015;21(24):8939-45doi: 10.1002/chem.201500524.
Storch, G., Spallek, M. J., Rominger, F., & Trapp, O. (2015). Tautomerization-mediated molecular switching between six- and seven-membered rings stabilized by hydrogen bonding. Chemistry (Weinheim an der Bergstrasse, Germany), 21(24), 8939-45. https://doi.org/10.1002/chem.201500524
Storch, Golo, et al. "Tautomerization-mediated molecular switching between six- and seven-membered rings stabilized by hydrogen bonding." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,24 (2015): 8939-45. doi: https://doi.org/10.1002/chem.201500524
Storch G, Spallek MJ, Rominger F, Trapp O. Tautomerization-mediated molecular switching between six- and seven-membered rings stabilized by hydrogen bonding. Chemistry. 2015 Jun 08;21(24):8939-45. doi: 10.1002/chem.201500524. Epub 2015 May 04. PMID: 25940593.
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Chemistry. 2015 Jun 08;21(24):8939-45. doi: 10.1002/chem.201500524. Epub 2015 May 04.

Tautomerization-mediated molecular switching between six- and seven-membered rings stabilized by hydrogen bonding.

Chemistry (Weinheim an der Bergstrasse, Germany)

Golo Storch, Markus J Spallek, Frank Rominger, Oliver Trapp

Affiliations

  1. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld?270, 69120 Heidelberg (Germany).
  2. Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld?270, 69120 Heidelberg (Germany). [email protected].

PMID: 25940593 DOI: 10.1002/chem.201500524

Abstract

1,3,4,6-Tetraketones typically undergo keto-enol tautomerism forming bis-enols stabilized by intramolecular hydrogen bonding in two six-membered rings. However, 1,3,4,6-tetraketones derived from the terpene ketone camphor and norcamphor exist as isomers with two distinguishable modes of intramolecular hydrogen bonding, namely, the formation of six- or seven-membered rings. The structural requirements for this so far unknown behavior were investigated in detail by synthesis and comparison of structural analogues. Both isomers of such 1,3,4,6-tetraketones were fully characterized in solution and in the solid state. Intriguingly, they slowly interconvert in solution by means of tautomerism-rotation cascades, as was corroborated by DFT calculations. The influence of temperature and complexation with the transition metals Pd, Rh, and Ir on the interconversion process was investigated.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: chelates; hydrogen bonds; ketones; molecular switches; tautomerism

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