Recent Advances in Stereospecific Transformations of Organoboron Reagents

ABSTRACT The development of stereospecific transformations of organoboron compounds has advanced rapidly over the past decade, driven by their exceptional configurational stability, tunable reactivity and broad functional group tolerance. Central to this progress is the use of ate complexes, generated by organolithium activation, which undergo highly enantiospecific reactions via either stereoretentive or stereoinvertive pathways. These strategies enable the efficient construction of new C–C, C–O, C–N, C–F, C–S and C–P bonds at stereogenic centres, often with complete preservation of enantiopurity. Reactivity can be further expanded through transmetalation to access more reactive organocopper and organozinc intermediates, unlocking transformations previously inaccessible to direct boronate chemistry. This review critically surveys recent advances in the stereospecific functionalisation of secondary, tertiary and polyboronic esters, emphasising applications in complex molecule synthesis and outlining key challenges ahead, including the stereocontrolled construction of quaternary centres, late‐stage diversification and underexplored heteroatom couplings.