Benzylic C(sp3)-C(sp2) cross-coupling of indoles enabled by oxidative radical generation and nickel catalysis

A mechanistically unique functionalization strategy for a benzylic C(sp(3))-H bond has been developed based on the facile oxidation event of indole substrates. This novel pathway was initiated by efficient radical generation at the benzylic position of the substrate, with subsequent transition metal catalysis to complete the overall transformation. Ultimately, an aryl or an acyl group could be effectively delivered from an aryl (pseudo)halide or an acid anhydride coupling partner, respectively. The developed method utilizes mild conditions and exhibits a wide substrate scope for both substituted indoles and C(sp(2))-based reaction counterparts. Mechanistic studies have shown that competitive hydrogen atom transfer (HAT) processes, which are frequently encountered in conventional methods, are not involved in the product formation process of the developed strategy.

Automated summary

A unique functionalization strategy for a benzylic C(sp(3))-H bond has been developed based on the facile oxidation event of indole substrates. The method utilizes mild conditions and exhibits a wide substrate scope for both substituted indoles and C(sp(2))-based reaction counterparts. Competitive hydrogen atom transfer processes, commonly seen in conventional methods, are not involved in the product formation process of this developed strategy.