10.1002/cctc.201701617
ChemCatChem
COMMUNICATION
Keywords: N-methylation • N-alkylation • cobalt-nanocatalyst •
In general stability, recycling and reusability of a given catalyst
are important features for the advancement of sustainable
industrial processes. Noticeably, this Co3O4/N@C-catalyst is
highly stable and conveniently recycled up to 5 times to
produced functionalized secondary amine (Fig. 4).
reductive amination • formic acid
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CF3
H
NO2
CHO
Co3O4/NGr@C
N
+
F3C
HCOOH, t-butanol
51
O
64
65
100 oC, 24h
O
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Figure 4. Recycling of Co3O4/NGr@C-catalyst for the preparation of
functionalized secondary amine. Reaction conditions: mmol 4-
5
nitroacetophenone, 7.5 mmol 4-(Trifluoromethyl)benzaldehyde, 400 mg
catalyst (4 mol% Co). 21.5 formic acid (4.3 equiv. as a HCOOH-Et3N (5:2)
mixture), 10 mL t-butanol, 100 oC, 24-30 h, yields were determined by GC
using 250 µL n-hexadecane standard.
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In summary, we have developed a selective and convenient
reductive amination process for the preparation of N-methyl and
- alkylamines using earth abundant cobalt-based nanocatalyst.
Starting from nitroarenes or amines and aqueous formaldehyde
or aldehydes, this operationally simple and cost-effective
protocol proceeds for the synthesis of structurally diverse and
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reductive N-methylation and -alkylation reactions have been
successfully performed.
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We thank Prof. Matthias Beller, Director, Leibniz Institute for
Catalysis for helpful discussions. The Federal Ministry of
Education and Research (BMBF), the State of Mecklenburg-
Vorpommern and the European Research Council are gratefully
acknowledged for general support. We thank analytical staff of
LIKAT, Prof. Angelika Brückner, Dr. Marga-Martina Pohl and Dr.
Jörg Radnik , Dr. Annette-Enrica Surkus for analytical data and
catalyst characterization.
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