Divergent Carbocyanation and Hydrocyanation of Alkynes Enabled by Photoinduced Nickel-Catalyzed Homolytic Bond Cleavage of C(sp3)-N Bond in Isonitriles

Catalytic strategies for breaking and forming chemical bonds are long-standing goals in chemical synthesis. However, the activation of inert chemical bonds remains a significant challenge. Recently, our group successfully developed a C(sp3)-N bond homolytic activation strategy of isonitriles using an in-situ generated, electronically active nickel complex. This strategy bypassed the thermodynamically unfavorable 2-electron or 1-electron oxidative addition processes, allowing us to invent the unprecedented “cut-and-sew” reaction using isonitriles and alkynes. This transformation proceeded under simple and mild conditions, demonstrating good substrate scope with excellent functional group compatibility and atom economy. Moreover, we can apply this activation mode to develop the selective hydrocyanation of alkynes with isonitriles as a cyanating agent in the presence of an exogenous photocatalyst.