Insights into the ruthenium-catalysed selective reduction of cardanol derivatives via transfer hydrogenation : a density functional theory study
MetadataShow full item record
The detailed mechanism for ruthenium-catalysed selective reductionof cardanol derivatives by transfer hydrogenation has been fully characterisedat the B3PW91-D3/ECP2/PCM//B3PW91/ECP1 level of density functional theory. Theexplored catalytic cycle involved the hydrogenation of the triene cardanolgiving the diene product through a highly stable η3-allylicintermediate via a kinetic barrier of 29.1 kcal mol−1, whichfollowed further hydrogenation leading to a more stable η3-allylicintermediate. The further reduction to the cardanol monoene product required anoverall barrier of 29.2 kcal mol−1, which offers a rationale for therequirement of elevated temperatures (refluxing isopropanol). The computedoverall barrier of 46.6 kcal mol−1 to accommodate a fully saturatedproduct is unsurmountable— in good agreement with the experiment, where no suchfull hydrogenation is observed, and rationalising the 100% selectivity towardsthe monoene product.
Ahmad , S , Crawford , E , Bilal , M , de Vries , J G & Buehl , M 2023 , ' Insights into the ruthenium-catalysed selective reduction of cardanol derivatives via transfer hydrogenation : a density functional theory study ' , Catalysis Science & Technology , vol. Advance articles . https://doi.org/10.1039/D3CY00135K
Catalysis Science & Technology
Copyright © 2023 The Author(s). Open Access Article. This article is licensed under aCreative Commons Attribution 3.0 Unported Licence.
DescriptionAuthors thank EaStCHEM and the School of Chemistry for their support.
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.