Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines.
Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.
State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian 116023 (China).
Min
M
Wang
State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian 116023 (China).
Jianmin
J
Lu
State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian 116023 (China).
Jiping
J
Ma
State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian 116023 (China).
Zhe
Z
Zhang
State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, Dalian 116023 (China). wangfeng@dicp.ac.cn.
Feng
F
Wang
copper; density functional calculations; heterocycles; heterogeneous catalysis; oxidation