Abstract
The tropylium catalyzed carboxylic acid O-H insertion with diazoesters providing α-hydroxy esters was reported recently through an activated carbene as the key intermediate. We report a revised mechanism involving a unique homoaromatic intermediate with the tropylium ion and the diazoester based on the DFT calculations. Our computational model provides a clear insight into the binding of the tropylium ion with the diazoester providing the homoaromatic intermediate. The reaction profiles of four different pathways were compared. The energies of the intermediates and the transition states are reported at B97-D3(SMD)/def2TZVP//B97-D3/def2TZVP (in dichloromethane). The energy profiles were compared across a few computational methods to study the sensitivity of our model across methods.
Supplementary materials
Title
Supplementary information - The Role of Homoaromaticity in the Tropylium-Catalyzed Carboxylic Acid O-H Insertion with Diazoesters
Description
Supplementary information - The Role of Homoaromaticity in the Tropylium-Catalyzed Carboxylic Acid O-H Insertion with Diazoesters
Contents: Computational Details; Table of Method Comparison - SCF Energies; Figures; Reaction Free-energy profiles; Raw Energy; Method Comparison plots; Cartesian Coordinates and SCF Energies
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