Jump to main content
Jump to site search


Selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes and methylamines from cyclic amines and CO2/H2 catalyzed by an ionic liquid–Pd/C system

Author affiliations

Abstract

The reduction of CO2 with amines and H2 generally produces N-formylated or N-methylated compounds over different catalysts. Herein, we report the selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes, and methylamines, which is achieved over an ionic liquid (IL, e.g., 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIm][BF4])–Pd/C catalytic system. By simply varying the reaction temperature, formamides and methylamines can be selectively produced, respectively, in high yields. Interestingly, 1,2-bis(N-heterocyclic)ethanes can also be obtained via the McMurry reaction of the formed formamide coupled with subsequent hydrogenation. It was found that [BMIm][BF4] can react with formamide to form a [BMIm]+–formamide adduct; thus combined with Pd/C it can catalyze McMurry coupling of formamide in the presence of H2 to afford 1,2-bis(N-heterocyclic)ethane. Moreover, Pd/C–[BMIm][BF4] can further catalyze the hydrogenolysis of 1,2-bis(N-heterocyclic)ethane to access methylamine. [BMIm][BF4]–Pd/C was tolerant to a wide substrate scope, giving the corresponding formamides, 1,2-bis(N-heterocyclic)ethanes or methylamines in moderate to high yields. This work develops a new route to produce N-methylamine and opens the way to produce 1,2-bis(N-heterocyclic)ethane from cyclic amine as well.

Graphical abstract: Selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes and methylamines from cyclic amines and CO2/H2 catalyzed by an ionic liquid–Pd/C system

Back to tab navigation

Supplementary files

Publication details

The article was received on 02 Jul 2019, accepted on 02 Sep 2019 and first published on 03 Sep 2019


Article type: Edge Article
DOI: 10.1039/C9SC03242H
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

  •   Request permissions

    Selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes and methylamines from cyclic amines and CO2/H2 catalyzed by an ionic liquid–Pd/C system

    R. Li, Y. Zhao, H. Wang, J. Xiang, Y. Wu, B. Yu, B. Han and Z. Liu, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC03242H

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements