Chao Zhou1,2, Tao Lei1,2, Xiang-Zhu Wei1,2, Chen Ye1,2, Zan Liu1,2, Bin Chen1,2, Chen-Ho Tung1,2, Li-Zhu Wu1,2. 1. Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China. 2. School of Future Technology, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
Abstract
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.
Transition-metal-catalyzed C-N bond-forming reactions have emerged as fundamental and powerful tools to construct n class="Chemical">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.