Striking AcOH Acceleration in Direct Intramolecular Allylic Amination Reactions

Abstract

An acid–base reaction to speed up a sluggish catalytic cycle! AcOH as the solvent enables extraordinarily fast and efficient PdII-catalysed, direct intramolecular allylic aminations, assisting the benzoquinone-mediated palladium reoxidation and ionisation of the intermediate palladium complexes (see scheme). The structural and energetic aspects of such a key step of the catalytic cycle are illustrated by means of a detailed DFT analysis.