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Insights into the ruthenium-catalysed selective reduction of cardanol derivatives via transfer hydrogenation : a density functional theory study

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Date
27/02/2023
Author
Ahmad, Shahbaz
Crawford, Ellis
Bilal, Muhammad
de Vries, Johannes G.
Buehl, Michael
Keywords
DFT
Hydrogenation
Homogeneous catalysis
Selective reduction
Transfer hydrogenation
QD Chemistry
DAS
MCP
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Abstract
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.
Citation
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
Publication
Catalysis Science & Technology
Status
Peer reviewed
DOI
https://doi.org/10.1039/D3CY00135K
ISSN
2044-4753
Type
Journal article
Rights
Copyright © 2023 The Author(s). Open Access Article. This article is licensed under aCreative Commons Attribution 3.0 Unported Licence.
Description
Authors thank EaStCHEM and the School of Chemistry for their support.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/27128

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