Mechanistic Studies on the Pauson-Khand Reaction
Computational efforts in the Kerr group are focused on providing mechanistic insight on various transition metal-mediated transformations. These computational studies serve to contextualise experimental observations and provide further evidence for the outcomes observed. In addition, we strive to find the optimal computational methodology in order to confidently predict selectivity and reactivity of processes under investigation.
In this regard, studies on the Pauson-Khand reaction (PKR) have been undertaken to ascertain why certain substrate classes react more efficiently than others. Experimental work has determined that substitution on the alkyne hinders reactivity (Scheme 1) but this cannot be explained by the proposed mechanism in the literature. Studies on new ligand spheres around the metal centre are being probed to determine a relationship between the structure of the substrate and its reactivity in the PKR.
Further work has focused on determining the reasoning for observed stereochemical outcomes when chiral substrates are used in the PKR. This involves the calculation of several different diastereomeric intermediates through the potential energy surface. Theoretical insight will help to determine which aspects are most important when attempting to control this stereochemistry. This area will contribute to a greater understanding of the reaction in order to increase its applicability and predictability.
This area of our research will serve to increase the confidence we have in predicting the preparative outcomes of our science and enhance the publication level of our experimental outputs overall.
For more information about the project contact William Kerr (firstname.lastname@example.org), Professor at the Department of Pure and Applied Chemistry at the University of Strathclyde, or Dr David Lindsay (email@example.com), Research Associate at the Department of Pure and Applied Chemistry at the University of Strathclyde.
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