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Issue 8, 1993
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Transfer hydrogenation of ketones with [Ru4H3(CO)12] as the precatalyst

Abstract

The cluster [N(PPh3)2][Ru4H3(CO)12]1a has been found to be an efficient precatalyst for the transfer hydrogenations of ketones and α,β-unsaturated ketones. With substrates such as (5S)-carvone [2-methyl-5-(1-methylethenyl)cyclohex-2-en-1-one], (3R)-methylcyclopentanone and (3R)-methylcyclohexanone, moderate to high diastereoselectivities were observed for reduction of the conjugated olefinic and ketonic functionalities respectively. Aromatisation of carvone to 5-isopropyl-2-methylphenol and disproportionation of cyclohex-2-en-1-one to phenol and cyclohexanone have also been found to be catalysed by 1a. Studies with radical inhibitors and other evidence suggest a radical mechanism for the transfer-hydrogenation and aromatisation reactions. In the transfer hydrogenation of cyclohex-2-en-1-one, the rate of conversion of 1a into other soluble species can be modelled accurately if autocatalysis is assumed. The time-dependent concentration profiles of cyclohex-2-en-1-one, cyclohexanone and cyclohexanol are simulated well if autocatalytic formation of an active intermediate followed by consecutive reactions leading to the formation of products is assumed. Such a model is also consistent with the proposed radical mechanism.

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Article type: Paper
DOI: 10.1039/DT9930001191
Citation: J. Chem. Soc., Dalton Trans., 1993,0, 1191-1199
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    Transfer hydrogenation of ketones with [Ru4H3(CO)12] as the precatalyst

    S. Bhaduri, K. Sharma and D. Mukesh, J. Chem. Soc., Dalton Trans., 1993, 0, 1191
    DOI: 10.1039/DT9930001191

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