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Issue 6, 2012
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Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers

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Abstract

Nine polyol stereoisomers ranging from three to six carbons in length were reacted under hydrogenolysis conditions (205–240 °C, 100 bar H2) over a Ru–C catalyst to better understand the reaction mechanism. Previous reports have postulated the retro-aldol mechanism as the main pathway leading to C–C scission. However, the retro-aldol mechanism was insufficient in explaining the product distribution of tetritols from pentitols, while the decarbonylation mechanism could explain the selectivity results of terminal C–C scission. Retro-aldol scission of internal C–C bonds was confirmed to occur by the tetritol product distribution from hexitols. Therefore, the presence or role of 3-keto and 4-keto intermediates had a negligible effect on the C–C hydrogenolysis of polyols when compared to aldehyde intermediates. The reaction rates of the polyols depended on the configuration of the polyol stereoisomers. The reactivity of the stereoisomers was correlated to the presence of erythro sequences of hydroxyl groups and was independent of the carbon chain length.

Graphical abstract: Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers

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Publication details

The article was received on 06 Jan 2012, accepted on 15 Mar 2012 and first published on 05 Apr 2012


Article type: Paper
DOI: 10.1039/C2GC00026A
Citation: Green Chem., 2012,14, 1635-1642
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    Probing the ruthenium-catalyzed higher polyol hydrogenolysis reaction through the use of stereoisomers

    K. L. Deutsch, D. G. Lahr and B. H. Shanks, Green Chem., 2012, 14, 1635
    DOI: 10.1039/C2GC00026A

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