Rh-Catalyzed Intermolecular Asymmetric Hydrofunctionalization of Alkenes

Rh-catalyzed asymmetric hydrofunctionalization of alkenes represents a pivotal strategy for constructing chiral heteroatom-containing compounds in organic synthesis. In recent years, this methodology has garnered significant attention, owing to its exceptional atom economy, high regioselectivity, and excellent stereocontrol. By facilitating the asymmetric addition of main-group element and hydrogen across alkenes, this approach enables the precise incorporation of carbon and diverse heteroatoms, including boron, silicon, nitrogen, oxygen, sulfur, and selenium, thereby substantially broadening the synthetic accessibility to chiral molecular architectures. Organized according to the categories of main-group elements, this review systematically summarizes recent advances in Rh-catalyzed enantioselective alkene hydrofunctionalization involving elements from Groups 13 to 16, with a focus on ligand design, expansion of reaction types, substrate scope, and synthetic applications. Finally, the current challenges in this field are discussed, and future research directions are outlined.