Catalysis with a Skip: Dynamically Coupled Addition, Proton Transfer, and Elimination During Au- and Pd-Catalyzed Diol Cyclization

31 May 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Au and Pd complexes have emerged as highly effective π-bond cyclization catalysts to construct heterocycles. These cyclization reactions are generally proposed to proceed through multi-step addition-elimination mechanisms involving Au- or Pd-alkyl intermediates. For Au- and Pd-catalyzed allylic diol cyclization, while the DFT potential energy surface landscapes show a stepwise sequence of alkoxylation π-addition, proton transfer, and water elimination, quasiclassical direct dynamics simulations reveal new dynamical mechanisms that depend on the metal center. For Au, trajectories reveal that after π-addition the Au-alkyl intermediate is always skipped because addition is dynamically coupled with proton transfer and water elimination. In contrast, for Pd catalysis, due to differences in the potential-energy landscape shape, only about half of trajectories show Pd-alkyl intermediate skipping. The other half of the trajectories show the traditional two-step mechanism with the intervening Pd-alkyl intermediate. Overall, this work reveals that interpretation of a DFT potential-energy landscape can be insufficient to understand catalytic intermediates and mechanisms and that atomic momenta through dynamics simulations is needed to determine if an intermediate is genuinely part of a catalytic cycle.


Direct Dynamics Trajectory Study


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.