Chromium‐Catalyzed Reductive C(sp ³ )‐Si/Ge Cross‐Electrophile Coupling of Dinitriles with Chlorosilanes and Chlorogermanes

ABSTRACT Organosilanes and organogermanes are valuable molecular motifs with broad applications in materials science, medicinal chemistry, and organic synthesis. However, efficient and general methods for constructing C(sp 3 )─Si and C(sp 3 )─Ge bonds from readily available electrophiles under mild conditions remain scarce. Herein, we report a chromium‐catalyzed reductive cross‐electrophile coupling of dinitriles with chlorosilanes to access a broad range of α‐silylated nitriles. The reaction employs a Cr(II)‐bipyridine catalyst with Mn(0) as a reductant, exhibiting excellent functional group tolerance and broad substrate scope. This protocol is successfully extended to C(sp 3 )─Ge bond formation using chlorogermanes, enabling the direct synthesis of alkylgermanes from alkyl electrophiles. Mechanistic investigations support an anionic mechanism. The synthetic utility of this strategy is demonstrated by gram‐scale reactions and late‐stage functionalization of bioactive molecules, offering a general platform for main‐group element functionalization via cross‐electrophile coupling.