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

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 int...

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Bibliographic Details
Main Authors: Storch, Golo (Author) , Spallek, Markus Jürgen (Author) , Rominger, Frank (Author) , Trapp, Oliver (Author)
Format: Article (Journal)
Language:English
Published: May 4, 2015
In: Chemistry - a European journal
Year: 2015, Volume: 21, Issue: 24, Pages: 8939-8945
ISSN:1521-3765
DOI:10.1002/chem.201500524
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/chem.201500524
Verlag, lizenzpflichtig, Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201500524
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Author Notes:Golo Storch, Markus J. Spallek, Frank Rominger, and Oliver Trapp
Description
Summary: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.
Item Description:Gesehen am 24.06.2020
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201500524

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