Talmazan, R. A., Refugio Monroy, J., del Rio Portilla, F., Castillo, I., & Podewitz, M. (2022). Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst. ChemCatChem, 14(20), Article e202200662. https://doi.org/10.1002/cctc.202200662
Development of C−N coupling methodologies based on Earth-abundant metals is a promising strategy in homogeneous catalysis for sustainable processes. However, such systems suffer from deactivation and low catalytic activity. We here report that encapsulation of Cu(I) within the phenanthroyl-containing calix[8]arene derivative 1,5-(2,9-dimethyl-1,10-phenanthroyl)-2,3,4,6,7,8-hexamethyl-p-tert-butylcalix[8]arene (C₈PhenMe₆) significantly enhances C−N coupling activity up to 92 % yield in the reaction of aryl halides and aryl amines, with low catalyst loadings (2.5 % mol). A tailored multiscale computational protocol based on Molecular Dynamics simulations and DFT investigations revealed an oxidative addition/reductive elimination process of the supramolecular catalyst [Cu(C₈PhenMe₆)I]. The computational investigations uncovered the origins of the enhanced catalytic activity over its molecular analogues: Catalyst deactivation through dimerization is prevented, and product release facilitated. Capturing the dynamic profile of the macrocycle and the impact of non-covalent interactions on reactivity allows for the rationalization of the behavior of the flexible supramolecular catalysts employed.
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Modeling and Simulation: 50% Structure-Property Relationsship: 50%