Chromium-Catalyzed Reductive C(sp3)-Si/Ge Cross-Electrophile Coupling of Dinitriles with Chlorosilanes and
Lin Ji1, Rui Wei1, Xiaoming Zeng1
1Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, China.
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(sp3)─Si and C(sp3)─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(sp3)─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.
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