Abstract
A computational approach has been developed to automatically generate and analyse the structures of the intermediates of palladium-catalysed carbon–hydrogen (C–H) activation reactions as well as to predict the final products. Implemented as a high-performance computing cluster tool, it has been shown to correctly choose the mechanism and rationalise regioselectivity of chosen examples from open literature reports. The developed methodology is capable of predicting reactivity of various substrates by differentiation between two major mechanisms – proton abstraction and electrophilic aromatic substitution. An attempt has been made to predict new C–H activation reactions. This methodology can also be used for the automated reaction planning, as well as a starting point for microkinetic modelling.
Highlights
Our knowledge of chemistry is enriched with new transformations that provide significant breakthroughs by enabling new synthetic strategies
A number of different mechanisms are proposed in the literature, explaining the experimental observations for C–H activation reactions, depending on the nature of a ligand (Ln) and transition metal (M) in the catalytically active species (LnM)
The key step for the electrophilic aromatic substitution is an electrophilic attack by Pd(II) onto the aromatic substrate that defines the regioselectivity of the overall process [24]
Summary
Our knowledge of chemistry is enriched with new transformations that provide significant breakthroughs by enabling new synthetic strategies Such examples in recent years include olefin metathesis [1] as well as C–C and C–N coupling reactions [2], among the most obvious examples. We demonstrate an approach that was developed to automate the DFT-level calculations of energies of the auto-generated reaction intermediates These results were further used to generalize mechanistic knowledge of a class of reactions, and the developed models were used for in silico prediction of reaction outcomes. A number of different mechanisms are proposed in the literature, explaining the experimental observations for C–H activation reactions, depending on the nature of a ligand (Ln) and transition metal (M) in the catalytically active species (LnM) These mechanisms include four elementary steps: oxidative addition, σ-bond metathesis, electrophilic substitution and 1,2-addition, respectively [15]. Using analysis of the computational data, a threshold to distinguish between two possible reaction mechanisms was established
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