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An efficient catalytic system was successfully developed on reduction of N‐heteroaromatics with H3N∙BH3 as hydrogen source in CuSO4 solution, featuring excellent chemoselectivity as well as very broad functional group tolerance. Various challenging substrates, such as OH‐, NH2‐, Cl‐, Br‐, etc., contained quinolines, quinoxalines, 1,5‐naphthyridines and quinazolines were all reduced smoothly. Mechanistic...