Chemoselective Hydrogenolysis of Tetrahydropyran‐2‐methanol to 1,6‐Hexanediol over Rhenium‐Modified Carbon‐Supported Rhodium Catalysts

Abstract Modification of Rh/C with Re species enabled chemoselective hydrogenolysis of tetrahydropyran‐2‐methanol to 1,6‐hexanediol. In particular, the Rh–ReO x /C (Re/Rh ratio=0.25) catalyst gave a high yield of 1,6‐hexanediol (84 %) and showed a very low activity for overhydrogenolysis to 1‐hexanol. Using the same catalyst in the hydrogenolysis of tetrahydrofurfuryl alcohol also gave a high yield of 1,5‐pentanediol (94 %). Characterization results indicate the formation of ReO x clusters attached on the surface of Rh metal particles. This can cause the synergy between ReO x and Rh, and the tetrahydropyran‐2‐methanol hydrogenolysis proceeds on the interface between Rh metal surface and attached ReO x species.