Mechanistic and Reactivity Insights into Diboron‐Mediated NN and NN Bond Scission

Diboron reagents have emerged as versatile reducing agents capable of transforming a broad range of functional groups through pathways like hydrogen‐ or metal–hydride‐based reductions. Moreover, the strong thermodynamic driving force for BO bond formation enables efficient cleavage of XO bonds and straightforward deoxygenation without the need for external hydrogen sources such as water or alcohol. This intrinsic reactivity can be further enhanced by bases or Lewis‐basic additives, including pyridines, which promote BB bond activation and broaden the scope of transformations accessible under mild conditions. The effectiveness of diboron‐mediated XO bond cleavage naturally raises the question of whether these reagents might also promote the scission of NN bondsa transformation of increasing interest due to the prevalence of NN motifs in synthetic intermediates, pharmaceuticals, and nitrogen‐rich frameworks. This review outlines current understanding of diboron‐mediated NN and NN bond cleavage and unifies mechanistic and reactivity insights to guide future advances in diboron‐based synthetic transformations.