New insights into the reactivity of aminomethylene derivatives of resorc[4]arene: amine group transfer, conformational analysis, reaction mechanism

Abstract

Using the example of aminomethylene derivatives of resorc[4]arene and their Michael reaction with 4-hydroxycoumarin, the possibility of transferring an amine molecule from substrate to product is demonstrated. The conformation of the aminocoumarin derivatives of resorc[4]arene formed is controlled by the polarity of the solvent. For one of the products, conformational analysis was performed by kinetic sampling using metadynamics (MTD). The energies of the final set of conformers were calculated by DFT (r2scan-3c). A reaction mechanism based on multiscale (ONIOM) Nudged Elastic Band (NEB-TS) reaction profile calculations is discussed.