NiH-Catalyzed Enantio- and Regioselective Hydroselenylation of Unactivated Alkenes.

Chiral alkyl selenides are valuable motifs in medicinal chemistry and redox-active molecular design, yet enantioselective hydroselenylation of unactivated alkenes remains challenging due to limited control over regio- and enantioselectivity. Here, we report nickel-hydride-catalyzed enantio- and regioselective hydroselenylation of unactivated alkenes directed by native amide groups using readily available diselenides. The method accommodates both terminal and internal alkenes as well as both aryl and alkyl diselenides, exhibiting broad functional-group tolerance and delivering structurally diverse chiral aliphatic selenides with high regio- and enantioselectivity under mild conditions. Mechanistic studies support enantiodetermining hydronickelation followed by single-electron diselenide activation and selective capture of the selenium radical by the chiral alkyl-nickel intermediate. This work establishes a general platform for asymmetric C─Se bond formation through the integration of NiH catalysis and radical selenium transfer.