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Herein, we report a heterogeneous TiO₂‐supported Re catalyst (Re/TiO₂) that promotes various selective hydrogenation reactions, which includes the hydrogenation of esters to alcohols, the hydrogenation of amides to amines, and the N‐methylation of amines, by using H₂ and CO₂. Initially, Re/TiO₂ was evaluated in the context of the selective hydrogenation of 3‐phenylpropionic acid methyl ester to afford 3‐phenylpropanol (p =5 MPa, T=180 °C), which revealed a superior performance over other catalysts that we tested in this study. In contrast to other typical heterogeneous catalysts, hydrogenation reactions with Re/TiO₂ did not produce dearomatized byproducts. DFT studies suggested that the high selectivity for the formation of alcohols in favor of the hydrogenation of aromatic rings is ascribed to the higher affinity of Re towards the COOCH₃ group than to the benzene ring. Moreover, Re/TiO₂ showed a wide …