Abstract
Reductive aminations are an essential class of reactions widely applied for the preparation of different kinds of amines, as well as a number of pharmaceuticals and industrially relevant compounds. In such reactions, carbonyl compounds (aldehydes, ketones) react with ammonia or amines in the presence of a reducing agent and form corresponding amines. Common catalysts used for reductive aminations, especially for the synthesis of primary amines, are based on precious metals or Raney nickel. However, their drawbacks and limited applicability inspired us to look for alternative catalysts. The development of base-metal nanostructured catalysts is highly preferable and is crucial to the advancement of sustainable and cost-effective reductive amination processes. In this protocol, we describe the preparation of carbon-supported cobalt-based nanoparticles as efficient and practical catalysts for synthesis of different kinds of amines by reductive aminations. Template synthesis of a cobalt–triethylenediamine–terephthalic acid metal–organic framework on carbon and subsequent pyrolysis to remove the organic template resulted in the formation of supported single cobalt atoms and nanoparticles. Applying these catalysts, we have synthesized structurally diverse benzylic, aliphatic and heterocyclic primary, secondary and tertiary amines, including pharmaceutically relevant products, starting from inexpensive and easily accessible carbonyl compounds with ammonia, nitro compounds or amines and molecular hydrogen. To prepare this cobalt-based catalyst takes 26 h, and the reported catalytic reductive amination reactions can be carried out within 18–28 h.
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Acknowledgements
We gratefully acknowledge the European Research Council (EU project 670986-NoNaCat) and the State of Mecklenburg-Vorpommern for financial and general support. We thank the analytical team of the Leibniz-Institute for Catalysis, Rostock, for their excellent service in the characterization of materials and reaction products.
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R.V.J., K.M. and M.B. planned and developed the project. K.M. prepared catalytic materials and performed the experiments. V.G.C. and T.S. co-performed the experiments. R.V.J., K.M. and M.B. wrote the manuscript. R.V.J. and M.B. supervised the project.
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Peer review information Nature Protocols thanks Bert Weckhuysen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Key references using this protocol
Jagadeesh, R. V., et al. Science, 358, 326–332 (2017): https://science.sciencemag.org/content/358/6361/326
Related protocol
Jagadeesh, R.V. et al. Nat Protoc. 10, 916–926 (2015): https://www.nature.com/articles/nprot.2015.049.
Integrated supplementary information
Supplementary Figure 1 TEM Images of Co/GS@C catalyst.
(A): EDXS map and STEM images of Co-DABCO-TPA@C-800 catalyst. EDXS map (left image): Cobalt = red, Oxygen = blue, Carbon = green. Black arrows highlight graphite embedded metallic Co particles (Middle image). White circles represent single Co atoms at carbon (right image). (B): EELS/EDXS study of Co-DABCO-TPA@C-800 catalyst. Left image= Parallel detected space-resolved Carbon (EELS), Nitrogen (EELS) and Cobalt (EDX) signals. Middle image = HAADF image overlaid by C/N elemental map at the position of measurement. Right image= Nitrogen K-edge EELS- spectrum of the white box in the middle image.
Supplementary Figure 2 TEM images of different supported cobalt catalysts.
(A) Co-DABCO-TPA@C-800, (B) Co-DABCO@C-800, (C) Co-TPA@C-800 and (D) Cobalt nitrate@C-800.
Supplementary Figure 3 ABF- and HAADF-STEM images of Co-DABCO-TPA@C materials pyrolyzed at different temperatures.
(A) Co-DABCO-TPA@C-1000, (B) Co-DABCO-TPA@C-600 and (C) Co-DABCO-TPA@C-400.
Supplementary Figure 4 HAADF-STEM/EDX images of cobalt nanocatalysts.
(A) Co-DABCO-TPA@C-800, (B) Co-DABCO@C-800, (C) Co-TPA@C-800 and (D) Cobalt nitrate@C-800.
Supplementary Figure 5
HAADF-STEM images of Co-DABCO-TPA MOF.
Supplementary Figure 6
HAADF-STEM image and EELS/EDX spectra of Co-DABCO-TPA MOF.
Supplementary Figure 7
XRD spectra of Co-DABCO-TPA@C materials pyrolyzed at different temperatures and recycled catalyst.
Supplementary Figure 8
XRD spectra of Co-TPA@C-800, Co-DABCO@C-800 and Cobalt nitrate@C-800.
Supplementary Figure 9
XRD spectra of Co-DABCO-TPA MOF (A&B) and Co-DABCO-TPA@C template (C).
Supplementary Figure 10 X-ray photoelectron spectra cobalt catalysts.
The Co2p (left) and N1s (right) electrons were probed in (A) Co-DABCO-TPA@C-800; (B) Co-TPA@C-800; (C) Co-DABCO@C-800.
Supplementary Figure 11 XP spectra of the Co 2p (A; left) and N1s (B; right) electrons for the catalysts: Co-DABCO-TPA@C materials unpyrolyzed and pyrolyzed at different temperatures.
Co-DABCO-TPA@C materials unpyrolyzed and pyrolyzed at different temperatures.
Supplementary Figure 12 Amount of Co and different N species depending on ligand.
The values were normalized to carbon amount.
Supplementary Figure 13
Amount of Co and different N species of Co-DABCO-TPA@C materials depending on pyrolysis temperatures normalized to carbon amount.
Supplementary information
Supplementary Information
Supplementary Figs. 1–13, Supplementary Methods 1 and 2, Supplementary Data 1 and 2.
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Murugesan, K., Chandrashekhar, V.G., Senthamarai, T. et al. Reductive amination using cobalt-based nanoparticles for synthesis of amines. Nat Protoc 15, 1313–1337 (2020). https://doi.org/10.1038/s41596-019-0258-z
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DOI: https://doi.org/10.1038/s41596-019-0258-z
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