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Metal-Free, Redox-Neutral, Site-Selective Access to Heteroarylamine via Direct Radical–Radical Cross-Coupling Powered by Visible Light Photocatalysis

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journal contribution
posted on 17.09.2020 by Chao Zhou, Tao Lei, Xiang-Zhu Wei, Chen Ye, Zan Liu, Bin Chen, Chen-Ho Tung, Li-Zhu Wu
Transition-metal-catalyzed C–N bond-forming reactions have emerged as fundamental and powerful tools to construct arylamines, a common structure found in drug agents, natural products, and fine chemicals. Reported herein is an alternative access to heteroarylamine via radical–radical cross-coupling pathway, powered by visible light catalysis without any aid of external oxidant and reductant. Only by visible light irradiation of a photocatalyst, such as a metal-free photocatalyst, does the cascade single-electron transfer event for amines and heteroaryl nitriles occur, demonstrated by steady-state and transient spectroscopic studies, resulting in an amine radical cation and aryl radical anion in situ for C–N bond formation. The metal-free and redox economic nature, high efficiency, and site-selectivity of C–N cross-coupling of a range of available amines, hydroxylamines, and hydrazines with heteroaryl nitriles make this protocol promising in both academic and industrial settings.