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Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics
Heng Song1, Yang Shen1, Hu Zhou1
1School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, P. R. China.
Abstract:
Triggering C-N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo- or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO)6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C-N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO)4(PPh3)2] (trans-W, PPh3 = triphenylphosphine) complex, which forms in situ via ligand replacement.
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