Mechanochemical deutero-dehalogenation of aryl halides and fluorosulfates with activated aluminum

Abstract

Deutero-dehalogenation offers a direct synthetic route to deuterated compounds; however, costly reductants as well as deuterium sources are usually required to generate reductive deutero-species. In this work, we reveal a solvent-free mechanochemical protocol that activates aluminum foil, seldom used as a reductant due to its dense oxide layer, for palladium-catalyzed deuteration of aryl halides with D₂O. This method achieves high yields (up to 98%) and deuterium incorporation (up to 0.97D_MS) within 60 minutes across diverse substrates. Mechanistic studies suggested that a unique in situ Al–D species was generated as the deuteron provider. This efficient and sustainable approach unlocks aluminum's potential, offering a versatile tool for rapid, selective deuterium labeling in organic synthesis.