Fragment-oriented design of catalysts based on the activation strain model

It is shown how a fragment approach toward analysing transition states (in terms of strained reactants that interact with each other: the Activation Strain model) provides a way of understanding the relative heights of reaction barriers and how this can be applied to achieving a more rational, fragment-oriented design of catalysts (FDC). The predictive value of the FDC approach is demonstrated in a computational application to Pd0-catalyzed C–X bond activation. It is shown how and why a model catalyst's stereochemical selectivity can be tuned towards retention or inversion of configuration of the carbon atom in the activated bond simply by omitting or introducing, respectively, anion assistance.