Alkoxide Trap in Transition‐Metal‐Catalyzed Dehydrogenative Coupling and Borrowing Hydrogen Reactions

Abstract Dehydrogenative coupling (DC) and borrowing hydrogen(ation) (BH) reactions are crucial in modern organic synthesis, offering efficient and sustainable ways to create valuable compounds. However, they often face a significant challenge: the alkoxide trap. This Concept explores the alkoxide trap in DC and BH reactions, starting with the basic mechanisms and the role of alkoxide intermediates. It then examines how the alkoxide trap leads to catalyst deactivation and reduced selectivity, influenced by thermodynamic and kinetic factors. To address this, we review recent advances in catalyst design, ligand engineering, and optimized reaction conditions, along with the use of in‐situ spectroscopy and computational modelling, to better understand the underlying processes and guide rational catalyst development. Furthermore, this Concept highlights the broad applicability of DC, and BH reactions across various substrates, underscoring the urgency of addressing the alkoxide trap issue to unlock their full synthetic potential.