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

Abstract

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.

Acknowledgments

We thank the Fonds der Chemischen Industrie (FCI) and the Netherlands Organization for Scientific Research (NWO-CW) for financial support.

Notes

In honour of Professor Nicholas C. Handy.

Additional information

Notes on contributors

F.M. Bickelhaupt *

In honour of Professor Nicholas C. Handy.