Photoredox/nickel dual-catalyzed reductive C(sp²)‒Si cross-coupling

Nickel-catalyzed cross-electrophile coupling of carbon-electrophiles and silicon-electrophiles has recently emerged as a powerful tool for C‒Si bond formations to synthesize highly valuable organosilanes. This reductive coupling strategy eliminates the manipulation of highly reactive organometallic reagents, thereby leading to a good functional group tolerance and a high step economy. However, the reported reductive C‒Si couplings have to use stoichiometric amounts of Zn or Mn dust as reductant, which somehow limits the synthetic application. Herein, we reported a novel cross-electrophile coupling of aryl halides with chlorosilanes enabled by a dual photoredox/nickel catalysis. Instead of using metallic reductants, a mild and readily available α-silylamine is selected as a reliable organic reductant. A variety of vinyl chlorosilanes and chlorohydrosilanes were coupled smoothly. This new catalytic protocol offers an alternative approach for facile access of organosilanes.