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Aprotic Amine-modified Manganese Dioxide Catalysts for Selectivity-tunable Oxidation of Amines
Authors:Qianqian Hao  Xiuquan Jia  Dr Jiping Ma  Mingxia Gao  Xiaomeng Fan  Jin Gao  Prof Jie Xu
Institution:1. Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001 P. R. China

State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 P. R. China;2. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 P. R. China;3. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 P. R. China

University of Chinese Academy of Sciences, Beijing, 100049 P. R. China

Abstract:Organic modifiers have shown promising potential for regulating the activity and selectivity of heterogeneous catalysts via tuning their surface properties. Despite the increasing application of organic modification technique in regulating the redox-acid catalysis of metal oxides, control of the acidity of metal oxide catalysts for enhanced reaction selectivity without sacrificing their redox activity remains a substantial challenge. Herein, we show the successful control of redox-acid catalysis of metal oxides with aprotic tertiary amine modifiers. Robust modification of manganese dioxide catalysts with N,N-dialkylcyclohexylamine selectively blocks the Lewis acid sites, with their redox activity mostly unaffected. This enables efficient synthesis of imines in high to excellent selectivity via aerobic oxidation of structurally diverse aryl amines.
Keywords:amines oxidation  aprotic modifier  imines  manganese dioxide  selectivity-tunable catalysis
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