Reductive amination using cobalt-based nanoparticles for synthesis of amines.
Journal
Nature protocols
ISSN: 1750-2799
Titre abrégé: Nat Protoc
Pays: England
ID NLM: 101284307
Informations de publication
Date de publication:
04 2020
04 2020
Historique:
received:
14
02
2019
accepted:
21
10
2019
pubmed:
24
3
2020
medline:
18
4
2020
entrez:
24
3
2020
Statut:
ppublish
Résumé
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.
Identifiants
pubmed: 32203487
doi: 10.1038/s41596-019-0258-z
pii: 10.1038/s41596-019-0258-z
doi:
Substances chimiques
Amines
0
Metal-Organic Frameworks
0
Cobalt
3G0H8C9362
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
1313-1337Références
Lawrence, S. A. Amines: Synthesis, Properties and Applications (Cambridge University Press, 2004).
Ricci, A. Amino Group Chemistry: From Synthesis to the Life Sciences (Wiley-VCH, 2008).
Smith, D. T., Delost, M. D., Qureshi, H. & Njarðarson, J. T. Top 200 pharmaceutical products by retail sales in 2016. https://njardarson.lab.arizona.edu/sites/njardarson.lab.arizona.edu/files/2016Top200PharmaceuticalRetailSalesPosterLowResV3_0.pdf (2017).
Roughley, S. D. & Jordan, A. M. The medicinal chemist’s toolbox: an analysis of reactions used in the pursuit of drug candidates. J. Med. Chem. 54, 3451–3479 (2011).
doi: 10.1021/jm200187y
Dewick, P. M. Medicinal Natural Products: A Biosynthetic Approach 3rd edn (John Wiley & Sons, 2008).
Yan, T., Feringa, B. L. & Barta, K. Direct N-alkylation of unprotected amino acids with alcohols. Sci. Adv. 3, eaao6494 (2017).
doi: 10.1126/sciadv.aao6494
Froidevaux, V., Negrell, C., Caillol, S., Pascault, J.-P. & Boutevin, B. Biobased amines: from synthesis to polymers; present and future. Chem. Rev. 116, 14181–14224 (2016).
doi: 10.1021/acs.chemrev.6b00486
Gomez, S. A., Peters, J. A. & Maschmeyer, T. The reductive amination of aldehydes and ketones and the hydrogenation of nitriles: mechanistic aspects and selectivity control. Adv. Synth. Catal. 344, 1037–1057 (2002).
doi: 10.1002/1615-4169(200212)344:10<1037::AID-ADSC1037>3.0.CO;2-3
Alinezhad, H., Yavari, H. & Salehian, F. Recent advances in reductive amination catalysis and its applications. Curr. Org. Chem. 19, 1021–1049 (2015).
doi: 10.2174/1385272819666150311233021
Wakchaure, V. N., Zhou, J., Hoffmann, S. & List, B. Catalytic asymmetric reductive amination of α‐branched ketones. Angew. Chem. Int. Ed. 49, 4612–4614 (2010).
doi: 10.1002/anie.201001715
Gallardo-Donaire, J. et al. Direct asymmetric ruthenium-catalyzed reductive amination of alkyl-aryl ketones with ammonia and hydrogen. J. Am. Chem. Soc. 140, 355–361 (2018).
doi: 10.1021/jacs.7b10496
Kadyrov, R. & Riermeier, T. H. Highly enantioselective hydrogen-transfer reductive amination: catalytic asymmetric synthesis of primary amines. Angew. Chem. Int. Ed. 42, 5472–5474 (2003).
doi: 10.1002/anie.200352503
Tax, X. et al. Asymmetric synthesis of chiral primary amines by ruthenium catalyzed direct reductive amination of alkyl aryl ketones with ammonium salts and molecular H
doi: 10.1021/jacs.7b12898
Chusov, D. & List, B. Reductive amination without an external hydrogen source. Angew. Chem. Int. Ed. 53, 5199–5201 (2014).
Ogo, S., Uehara, K., Abura, T. & Fukuzumi, S. pH-Dependent chemoselective synthesis of α-amino acids. Reductive amination of α-keto acids with ammonia catalyzed by acid-stable iridium hydride complexes in water. J. Am. Chm. Soc. 126, 3020–3021 (2004).
doi: 10.1021/ja031633r
Nakamura, Y., Kon, K., Touchy, A. S., Shimizu, K.-i & Ueda, W. Selective synthesis of primary amines by reductive amination of ketones with ammonia over supported Pt catalysts. ChemCatChem 7, 921–924 (2015).
doi: 10.1002/cctc.201402996
Gross, T., Seayad, A. M., Ahmad, M. & Beller, M. Synthesis of primary amines: first homogeneously catalyzed reductive amination with ammonia. Org. Lett. 4, 2055–2058 (2002).
doi: 10.1021/ol0200605
Gallardo-Donaire, J., Ernst, M., Trapp, O. & Schaub, T. Direct synthesis of primary amines via ruthenium‐catalysed amination of ketones with ammonia and hydrogen. Adv. Synth. Catal. 358, 358–363 (2016).
doi: 10.1002/adsc.201500968
Liang, G. et al. Production of primary amines by reductive amination of biomass derived aldehydes/ketones. Angew. Chem. Int. Ed. 56, 3050–3054 (2017).
doi: 10.1002/anie.201610964
Wang, Z. Mignonac reaction. in Comprehensive Organic Name Reactions and Reagents (John Wiley & Sons, 2010).
Mao, F. et al. Heterogeneous cobalt catalysts for reductive amination with H
doi: 10.1039/C6RA21415K
Santoro, F., Psaro, R., Ravasio, N. & Zaccheria, F. Reductive amination of ketones or amination of alcohols over heterogeneous Cu catalysts: Matching the catalyst support with the N‐alkylating agent. ChemCatChem 4, 1249–1254 (2012).
doi: 10.1002/cctc.201200213
Jagadeesh, R. V. et al. Hydrogenation using iron oxide–based nanocatalysts for the synthesis of amines. Nat. Protoc. 10, 548–557 (2015).
doi: 10.1038/nprot.2015.025
Jagadeesh, R. V. et al. Cobalt-based nanocatalysts for green oxidation and hydrogenation processes. Nat. Protoc. 10, 916–926 (2015).
doi: 10.1038/nprot.2015.049
Jagadeesh, R. V. et al. MOF-derived cobalt nanoparticles catalyze a general synthesis of amines. Science 358, 326–332 (2017).
doi: 10.1126/science.aan6245
Hahn, G., Kunnas, P., de Jonge, N. & Kempe, R. General synthesis of primary amines via reductive amination employing a reusable nickel catalyst. Nat. Catal. 2, 71–77 (2019).
doi: 10.1038/s41929-018-0202-6
Filipponi, L. & Sutherland, D.S. Nanotechnologies: Principles, Applications, Implications and Hands-on Activities (European Commission, European Union, 2012).
Polshettiwar, V. & Asefa, T. Nanocatalysis: Synthesis and Applications (John Wiley & Sons, 2013).
Sankar, M. et al. Designing bimetallic catalysts for a green and sustainable future. Chem. Soc. Rev. 41, 8099–8139 (2012).
doi: 10.1039/c2cs35296f
Manoj., B. G. et al. Core-shell nanoparticles: synthesis and applications in catalysis and electrocatalysis. Chem. Soc. Rev. 44, 7540–7590 (2015).
doi: 10.1039/C5CS00343A
Munnik, P., de Jong, P. E. & de Jong, K. P. Recent developments in the synthesis of supported catalysts. Chem. Rev. 115, 6687–6718 (2015).
doi: 10.1021/cr500486u
Tao, F. Metal Nanoparticles for Catalysis: Advances and Applications (Royal Society of Chemistry, 2014).
van Schrojenstein Lantman, E. M., Deckert-Gaudig, T., Mank, A. J. G., Deckert, V. & Weckhuysen, B. M. Catalytic processes monitored at the nanoscale with tip-enhanced Raman spectroscopy. Nat. Nanotechnol. 7, 583–586 (2012).
doi: 10.1038/nnano.2012.131
Jagadeesh, R. V. et al. Nanoscale Fe
doi: 10.1126/science.1242005
Liu, L. & Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018).
doi: 10.1021/acs.chemrev.7b00776
Wang, A., Li, J. & Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2, 65–81 (2018).
doi: 10.1038/s41570-018-0010-1
Chen, Y. et al. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2, 242–1264 (2018).
Yan, N. & Dyson, P. J. Nanocatalysis: synthesis, characterization, application and mechanisms. Catal. Today 183, 1–178 (2012).
doi: 10.1016/j.cattod.2011.12.019
Dang, S., Zhu, Q.-L. & Xu, Q. Nanomaterials derived from metal-organic frameworks. Nat. Rev. Mat. 3, 17075 (2017).
doi: 10.1038/natrevmats.2017.75
Shen, K., Chen, X., Chen, J. & Li, Y. Development of MOF-derived carbon-based nanomaterials for efficient catalysis. ACS Catal. 6, 5887–5903 (2016).
doi: 10.1021/acscatal.6b01222
Buchner, F. et al. Coordination of iron atoms by tetraphenylporphyrin monolayers and multilayers on Ag(111) and formation of iron-tetraphenylporphyrin. J. Phys. Chem. C. 112, 15458–15465 (2008).
doi: 10.1021/jp8052955
Jaouen, F. et al. Cross-laboratory experimental study of non-noble-metal electrocatalysts for the oxygen reduction reaction. ACS Appl. Mater. Interfaces 1, 1623–1639 (2009).
doi: 10.1021/am900219g