Due to limited mechanistic insights, catalyst design and optimization in transition metal catalysis are often based on chemical intuition. I will discuss two examples in which computations have revealed novel and counterintuitive mechanistic understanding that refined the catalyst design principles: (1) In transition-metal catalyzed C-H and C-C bond functionalization reactions, significant amount of previous research has focused on the mechanism and selectivity of the initial C-H/C-C bond cleavage (metalation) step. Our computational studies have indicated that a number of experimentally observed reactivity and selectivity trends are indeed originated in the subsequent functionalization of the C-H/C-C metalated intermediate, rather than in the metalation step itself. (2) We developed a Ligand-Substrate Interaction Model to reveal the nature of the through-bond and through-space interactions between the metal catalyst and the substrate and to predict the effects of such interactions on reactivity and selectivity. Although the conventional understanding of the non-bonding interaction between ancillary ligand and substrate is mainly steric repulsions, we have demonstrated the stabilizing dispersion interactions between the substrate and bulky bisphosphine ligand promote the Cu-catalyzed hydroamination of unactivated aliphatic olefins.

Computational studies of functionalization of C-H, C-C bonds and olefins

256th National Meeting (2018)

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