A TEMPO‐Free Copper‐Catalyzed Aerobic Oxidation of Alcohols |
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Authors: | Boran Xu Prof Jean‐Philip Lumb Prof Bruce A Arndtsen |
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Institution: | Department of Chemistry, McGill University, 801 Sherbrooke St. West Montreal, Quebec, H3A 0B8 (Canada) |
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Abstract: | The copper‐catalyzed aerobic oxidation of primary and secondary alcohols without an external N‐oxide co‐oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N‐methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6‐tetramethyl‐l‐piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un‐activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. |
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Keywords: | aerobic oxidation alcohols biomimetic catalysis copper tyrosinase |
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