The self-assembled supramolecular cage catalyst 12-[Ga4L6 ] (L=N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphtha-lene) significantly increases the reaction rate of Nazarov cyclization of 1,3-pentadienols by over a million times compared to the background reaction. The classical molecular dynamics(MD) calculation and quantum chemical calculations(DFT) were carried out to study the role of catalyst cage of the reaction.
The configurations of the intermediates with explicit solvent water molecules were simulated with molecular dynamics calculations, and the resulting frames of the dynamics calculations were clustered based on RMSD. Representative structures were further selected to perform DFT calculation.
The free energy differences were compared for each intermediate with or without the cage catalyst. The barrier of protonation step is lower by 15kcal/mol with the cage catalyst than without the catalyst. The barrier of the cyclization step after water loss is very little upon encapsulation.

Computational study on large rate enhancements of Nazarov cyclization in supramolecular catalyst

ACS Fall 2020 Virtual Meeting

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