Harsh P. Chavda, Kevin J. Liang, Tanner J. Megna, Olivia R. Taylor, Grace Kim, Angie L. López, Ana Bahamonde
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Indole Photocatalysts and Secondary Amine Ligands Enable Nickel-Photoredox C(sp2)–Heteroatom Couplings
Nickel-photochemical C(sp2)–heteroatom coupling reactions have emerged as a powerful tool for constructing diverse molecular architectures. However, most existing methods rely on expensive photocatalysts or specialized ligands, limiting their practicality and scalability. Here, we introduce a photocatalytic initiation strategy driven by inexpensive indoles, eliminating the need for designer photocatalysts. Additionally, we demonstrate the effectiveness of highly tunable secondary amine ligands in facilitating coupling while suppressing side reactions that sequester the Ni catalyst off-cycle. Our approach enables a broad range of amination and etherification reactions with good yields and functional group tolerance, providing a scalable platform for C–N and C–O couplings that relies on a readily available photocatalyst and cost-effective, modular ligands. Finally, mechanistic investigations suggest that the reaction operates via an unconventional aryl radical-initiated Ni(I/III) catalytic cycle, distinguishing it from traditional Ni-photoredox processes. This initiation mode, in which aryl radicals are generated under mild conditions compatible with organometallic catalysis, is expected to serve as a generalizable platform for other synthetic transformations beyond Ni-catalyzed processes.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.