Biomimetic formation of 2-tropolones by dioxygenase-catalysed ring expansion of substituted 2,4-cyclohexadienones
Xin, Meite and Bugg, Tim. (2010) Biomimetic formation of 2-tropolones by dioxygenase-catalysed ring expansion of substituted 2,4-cyclohexadienones. ChemBioChem, Vol.11 (No.2). pp. 272-276. ISSN 1439-4227Full text not available from this repository.
Official URL: http://dx.doi.org/10.1002/cbic.200900631
Substituted 2-tropolone natural products, are found in plants and fungi. Their biosynthesis is thought to occur by ring expansion from a cyclohexadienone precursor, but this reaction has not previously been demonstrated experimentally. Treatment of 6-hydroxy-6-hydroxymethylcyclohexa-2,4-dienone with the non-haem iron(II)-dependent extradiol catechol dioxygenase MhpB from Escherichia coli results in the formation of the 2-tropolone ring-expansion product through a pinacol-type rearrangement. Three further substituted cyclohexa-2,4-dienone analogues were prepared, and treatment of each analogue was found to give the substituted 2-tropolone ring-expansion product. This ring expansion could also be effected nonenzymatically by treatment with. 1,4,7-triazacyclonone and FeCl2. This is a novel transformation for non-haem iron-dependent enzymes, and this is the first experimental demonstration of the proposed ring-expansion reaction in tropolone biosynthesis.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry
Q Science > QP Physiology
|Divisions:||Faculty of Science > Chemistry|
|Library of Congress Subject Headings (LCSH):||Biomimetics, Pinacol rearrangement, Ring formation (Chemistry), Biosynthesis|
|Journal or Publication Title:||ChemBioChem|
|Publisher:||Wiley - V C H Verlag GmbH & Co. KGaA|
|Official Date:||25 January 2010|
|Number of Pages:||5|
|Page Range:||pp. 272-276|
|Access rights to Published version:||Restricted or Subscription Access|
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