Mechanochemical Deutero-Dehalogenation of Aryl Halides and Fluorosulfates with Activated Aluminum

Abstract

Deutero-dehalogenation offers a direct route to deuterated compounds, however, costly reductants as well as deuterium sources are usually involved providing reductive deutero-speices. In this work, we unveiled a solvent-free mechanochemical protocol that activates aluminum foil, seldom used as a reductant due to its densely oxide layer, for palladium-catalyzed deuteration of aryl halides with D₂O. This method achieves high yields (up to 98%) and deuterium incorporation (up to 0.97 D_MS) within 60 minutes across diverse substrates. Mechanistic studies suggested 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.