title: C-N and N-H Bond Metathesis Reactions Mediated by Carbon Dioxide.
abstract: Herein, we report CO2 -mediated metathesis reactions between amines and DMF to synthesize formamides. More than 20 amines, including primary, secondary, aromatic, and heterocyclic amines, diamines, and amino acids, are converted to the corresponding formamides with good-to-excellent conversions and selectivities under mild conditions. This strategy employs CO2 as a mediator to activate the amine under metal-free conditions. The experimental data and in situ NMR and attenuated total reflectance IR spectroscopy measurements support the formation of the N-carbamic acid as an intermediate through the weak acid-base interaction between CO2 and the amine. The metathesis reaction is driven by the formation of a stable carbamate, and a reaction mechanism is proposed.
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Yehong
authors.initials: Y
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Jing
authors.initials: J
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).|University of the Chinese Academy of Sciences, No.19A Yuquan Road, Beijing 100049 (PR China).
authors.forename: Chaofeng
authors.initials: C
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Zhixin
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China). xujie@dicp.ac.cn.
authors.forename: Jie
authors.initials: J
authors.lastname: Xu
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Shutao
authors.initials: S
authors.lastname: Xu
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China).
authors.forename: Fangjun
authors.initials: F
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Catalysis (SKLC), Dalian National Laboratory for Clean Energy (DNL), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023 (PR China). wangfeng@dicp.ac.cn.
authors.forename: Feng
authors.initials: F
authors.lastname: Wang
mesh_terms: D000388:Air; D000588:Amines / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D004126:Dimethylformamide / Q000737:chemistry*; D007700:Kinetics
chemical_list: D000588:Amines; D002245:Carbon Dioxide; D004126:Dimethylformamide
keywords: carbon dioxide; formamide; metathesis; reaction mechanisms; synthetic methods