Switching Radical Fate for Chemodivergent C–C and C–N Bond Formation on β-Carbolines from Feedstock Hydrocarbons and Cyclic Ethers

We report a reagent-controlled cross-dehydrogenative coupling strategy for chemodivergent (sp3)C-C(sp2) or C(sp3)-N bond formation on β-carbolines using feedstock hydrocarbons and cyclic ethers. Mechanistic studies reveal reagent-dependent control over the hydrocarbon radical fate in selective and programmable C-C or C-N bond construction without prefunctionalization of starting materials. This approach provides rapid access to diverse C1- and N9-functionalized β-carboline libraries with broad substrate scope and high chemoselectivity, bypassing traditional multistep sequences and premodified starting materials.