Mechanochemical Birch Reduction with Low Reactive Alkaline Earth Metals

Abstract Birch reduction and similar dissolved metal‐type transformations hold significant importance in the organic synthesis toolbox. Historically, the field has been dominated by alkali metal reductants. In this study, we report that largely neglected, low‐reactive alkaline earth metals can become powerful and affordable reductants when used in a ball mill under essentially solvent‐free conditions, in the presence of ethylenediamine and THF as liquid additives. Calcium can reduce both electron‐deficient and electron‐rich arenes, with yields of products similar to those obtained with lithium metal. Magnesium reveals enhanced reducing power, enabling the reduction of benzoic acids while keeping electron‐rich aromatic moieties intact and allows for chemoselective transformations. The developed mechanochemical approach uses readily available and safer‐to‐handle metals, operates under air and ambient temperature conditions, and can be used for gram‐scale preparations. Finally, we demonstrate that the developed conditions can be used for other dissolved metal‐type reductive transformations, including reductive amination, deoxygenation, dehalogenation, alkene and alkyne reductions.