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.
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Nahra et al. (2009) studied this question.
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