Article, 2024

Light-Switchable N-Alkylation Using Amine-Functionalized MOF

Applied Catalysis B Environmental, ISSN 1873-3883, 0926-3373, Volume 350, Page 123924, 10.1016/j.apcatb.2024.123924

Contributors

Huang, Yue [1] [2] [3] Li, Yaru (Corresponding author) [4] [5] Zhang, Dongsheng 0000-0001-9839-4973 [1] [2] Mai, Yuanqiang [1] Besenbacher, Flemming [6] Dong, Chuan [3] Rosei, Federico F 0000-0001-8479-6955 [7] Yang, Yong [2] [5] Li, Yong-Wang 0000-0002-0573-042X [2] [5] Niemantsverdriet, Hans J W 0000-0002-0743-0850 [2] [8] Liang, Wen Ting 0000-0002-3275-9965 (Corresponding author) [3] Su, Ren (Corresponding author) [1] [2]

Affiliations

  1. [1] Soochow Institute for Energy and Materials Innovations (SIEMIS), Suzhou 215006, China
    2. [NORA names: China; Asia, East];
  2. [2] SynCat@Beijing, Synfuels China Technology Co. Ltd., Huairou, Beijing 101407, China
    3. [NORA names: China; Asia, East];
  3. [3] Shanxi University
    4. [NORA names: China; Asia, East];
  4. [4] Zhengzhou University
    5. [NORA names: China; Asia, East];
  5. [5] Institute of Coal Chemistry
    6. [NORA names: China; Asia, East];

Abstract

Catalytic N-alkylation is a frequently employed method to synthesize secondary amines and imines, yet selectivity control remains as a challenge that normally requires specialized catalysts under harsh reaction conditions. Here we propose a light-switchable N-alkylation of amines with aromatic halides for selective synthesis of secondary amines and imines, using an amine-functionalized metal-organic framework (MIL-125-NH2) under mild conditions. The MIL-125-NH2 catalyst possesses Lewis acidic sites, which catalyze direct dehalogenative condensation of bromides with primary amines to produce secondary amines in the dark. Upon irradiation, the MIL-125-NH2 reduces molecular oxygen to create oxygen radicals, converting bromides into the corresponding aldehydes to yield imines via a dehydrative coupling with amines. With appropriate acidity, rapid oxygen reduction kinetics, and optimized adsorption of aromatic bromides and generated water, the system catalyzes the conversion of a wide range of substrates, thus featuring it a promising method for applications.

Keywords

Lewis, Lewis acid sites, MIL-125-NH2, MOF, N-alkylation, acid, acid sites, aldehydes, amine-functionalized MOF, amine-functionalized metal-organic framework, amines, applications, aromatic bromides, aromatic halides, bromide, catalyst, condensation, conditions, conversion, coupling, dark, dehydrative coupling, framework, halides, harsh reaction conditions, imine, irradiation, kinetics, metal-organic frameworks, method, mild conditions, molecular oxygen, optimal adsorption, oxygen, oxygen radicals, oxygen reduction kinetics, primary amines, radicals, reaction conditions, reduction kinetics, secondary amines, sites, specialized catalysts, substrate, synthesis, synthesis of secondary amines, system, water, yield imines

Funders

  • National Natural Science Foundation of China

Data Provider: Digital Science

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