David Sanchez Roa, Robert E. Mulvey, Eva Hevia
Alkali-metal compounds, particularly organolithium and lithium amide reagents, are indispensable organometallic reagents in synthesis, finding widespread applications in cornerstone stoichiometric organic processes. Recent advances in the development of heavier alkali-metal analogues have revealed their emerging potential not only to participate in stoichiometric processes but also to catalyze transformations traditionally dominated by precious transition metals. This perspective provides an overview of a selection of these applications focusing on hydrogen isotope exchange, alkene isomerization, C–C bond formation, hydrophosphination, and hydrogenation. Special focus is placed on current mechanistic understanding and alkali-metal effects, aiming to draw out key challenges and opportunities that may guide the future development of alkali-metal-mediated catalysis.