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Issue 32, 2013
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The mechanism for the hydrogenation of ketones catalyzed by Knölker's iron-catalyst

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Abstract

Knölker's iron-based catalysts have some value in “green” transformations given the relatively low toxicity of iron compared to more commonly used precious-metal catalysts. Density functional methods have been used to extensively explore the use of an iron catalyst for hydrogen-transfer processes. Several inner- (with substrate coordination) and outer-sphere mechanisms (with no substrate coordination) were analyzed using a semi-simplified system. An outer-sphere route involving a concerted hydrogen-transfer to the substrate was found to be the most kinetically feasible mechanism, with a free energy barrier of only 10.2 kcal mol−1. This mechanism was then used to explore the complete system at the same theoretical level. The real system had a higher free energy barrier (20.7 kcal mol−1) which is due to the steric effect of the substituent group. All the calculated results were in good agreement with the experimental results.

Graphical abstract: The mechanism for the hydrogenation of ketones catalyzed by Knölker's iron-catalyst

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Publication details

The article was received on 03 May 2013, accepted on 07 Jun 2013 and first published on 11 Jun 2013


Article type: Paper
DOI: 10.1039/C3OB40936H
Citation: Org. Biomol. Chem., 2013,11, 5264-5277
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    The mechanism for the hydrogenation of ketones catalyzed by Knölker's iron-catalyst

    X. Lu, Y. Zhang, P. Yun, M. Zhang and T. Li, Org. Biomol. Chem., 2013, 11, 5264
    DOI: 10.1039/C3OB40936H

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