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

Shahbaz Ahmad, Ellis Crawford, Muhammad Bilal, Johannes G. de Vries, Michael Buehl*

*Corresponding author for this work

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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. The explored 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, which followed further hydrogenation leading to a more stable η3-allylicintermediate. The further reduction to the cardanol monoene product required an overall barrier of 29.2 kcal mol−1, which offers a rationale for the requirement of elevated temperatures (refluxing isopropanol). The computed overall barrier of 46.6 kcal mol−1 to accommodate a fully saturated product is unsurmountable— in good agreement with the experiment, where no such full hydrogenation is observed, and rationalising the 100% selectivity towards the monoene product.

Original languageEnglish
Pages (from-to)2662-2674
Number of pages13
JournalCatalysis Science & Technology
Volume13
Issue number9
Early online date27 Feb 2023
DOIs
Publication statusPublished - 7 May 2023

Keywords

  • DFT
  • Hydrogenation
  • Homogeneous catalysis
  • Selective reduction
  • Transfer hydrogenation

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