Asymmetric Transition-Metal-Catalyzed Hydrofunctionalization of Alkenylmetalloids (B, Si, and Ge)

Asymmetric hydrofunctionalization of alkenylmetalloids has emerged as a powerful strategy for the direct construction of chiral organometalloid compounds with high levels of regio-, chemo-, and stereocontrol. In contrast to classical approaches that rely on preformed organometallic reagents or stoichiometric chiral auxiliaries, transition-metal-catalyzed hydrofunctionalization enables an atom-economical access to structurally diverse enantioenriched boron-, silicon-, and germanium-containing building blocks from simple alkenyl or even alkynyl precursors. This Review highlights recent advances in the reductive coupling of alkenylmetalloids with particular emphasis on transformations leading to geminal and vicinal diheteroatom-substituted chiral motifs. The synthetic value of these methodologies is highlighted by streamlined derivatizations and applications in natural product synthesis and pharmaceutical development. Together, these advances position alkenylmetalloid hydrofunctionalization as a conceptually unifying and transformative strategy for asymmetric synthesis, redefining how complex chiral organometalloid architectures can be constructed from simple unsaturated feedstocks.