Naturalproductman’s Blog

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C-H Oxidation

Posted by naturalproductman on June 27, 2009

Miquel Costas and Xavi Ribas et al at the Universitat de Girona in Spain has recently published in ACIEE on a iron-catalyzed (1 mol%) aliphatic C-H oxidation of alkanes using hydrogen peroxide as the oxidant.  What’s notable is that these Fe catalyzed oxidations can be found in nature (ie:  cytochrome P450’s) and I wouldn’t be surprised if they were originally inspired to use iron because of iron’s occurence in nature.

fe catalysis

ACIEE paper

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2 Responses to “C-H Oxidation”

  1. Edinburgher said

    Just to prepare the catalyst is difficult actually. Fe(II) and Fe(III) are quite tough to work with.

    Is the reaction stereoselective BTW, and to what extent?

    • naturalproductman said

      Good point: these reactions are indeed stereoselective and more specifically, they are stereospecific since stereospecific reactions are a subset of stereoselective ones.

      Interestingly, they do explain in the paper that because of the stereospecificity of the reactions, long-lived radical type intermediates are not involved. However, the C-H bond strength indicates site selectivity since they only see hydroxylation at tertiary carbon centers in the presence of secondary ones. Steric and electronic factors also seem to play a role in site oxidation.

      In the supporting information they show the GC chiral column chromatogram of the product distribution for the cis-1,2-dimethylcyclohexane meso starting material.

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