645
SiO 2 and Co/SiO 2 catalysts for the reductive amination of FUR was similar to noble
metal Ru/SiO 2 catalyst with FAM yield of 94, 93, and 90% under the conditions of
750 psi H 2 and 403 K for 10 h [119].
2.3.2 Reductive Amination of HMF
The reductive amination of HMF can produce N-substituted-5-(hydroxymethyl)-2furfuryl amines with pharmaceutical functions such as calcium antagonistic activity, cholinergic agent, antimuscarinic agent, and carcinogenesis inhibitors. Zhu
et al. used rutile titania-supported gold (Au/TiO 2 -R) catalyst to catalyze the reductive amination of HMF using Co and water as inexpensive reductant [120]. The
yield of 2,5-bis-(hydroxymethyl)furan (BHMF) reached to 93% within 2.5 h at
333 K under 20 bar CO in the presence of water/methanol (1:1). Recently, GarcíaOrtiz et al. investigated the reductive amination of HMF in the presence of Pd/C as
a catalyst using various amines and ammonia as an amine source, as well as nitrobenzene in the one-pot reaction, where N-substituted-5-(hydroxymethyl)-2-furfuryl
amines were obtained in excellent yield [124]. Furthermore, Karve et al. reported
active palladium-functionalized MOF/polymer composite (UiO-67/PpPDA/Pd) for
the reductive amination of HMF with different aliphatic and aromatic amines exhibiting electron-withdrawing or electron-donating groups [121]. A 94.5% yield for the
desired amine was obtained at 323 K under 5 MPa H 2 after 2 h in the presence of
aniline as a substrate and ethanol as a solvent (Table 6). Also, the catalyst showed
high recyclability of up to 15 cycles, which was associated with the addition of
polymer poly-para-phenylenediamine (PpPDA), which prevents the aggregation
Table 6 Summary of reductive amination of furanics over different nanocomposite catalysts
Reaction condition
Reactant Product Catalyst
Performance
Refs.
Conv.
(%)
Yield
(%)
353 K, 2 h, 2 MPa H 2 , 28% aq.
NH 3
FU
FAM
Rh/Al 2 O 3
100
92
[116]
373 K, 15 min, 3 MPa H 2 , NH 3
sol.
FU
FAM
Ru/
HZSM-5(46)
NA
75
[117]
393 K. 2 h, 0.1 MPa NH 3 and
1 MPa H 2
FU
FAM
Raney Co
100
98.9
[118]
403 K, 10 h, 5.17 MPa H 2 ,
1 mL NH 4 OH
FU
FAM
Ni/SiO 2 and Co/
SiO 2
100
90–94 [119]
363 K, 10 h, 4 MPa CO, amines
(0.5 mmol)
HMF
BHMF Au/TiO 2 -R
>99
93
[120]
323 K, 2 h, 5 MPa H 2 , aniline
(0.24 mmol)
HMF
Amine UiO-67/PpPDA/
Pd
100
94.5
[121]
373 K, 6 h, 0.1 MPa H 2 , NH 3
HMF
FAA
Ni 6 Al 1 O x
100
98
[122]
373 K, 4 h, 2 MPa H 2 , aq. NH 3
(5 mL)
HMF
AMF
Ni/SBA-15
NA
89.8
[123]
Efficient Nanocomposite Catalysts for Sustainable Production of Biofuels and…
SiO 2 and Co/SiO 2 catalysts for the reductive amination of FUR was similar to noble
metal Ru/SiO 2 catalyst with FAM yield of 94, 93, and 90% under the conditions of
750 psi H 2 and 403 K for 10 h [119].
2.3.2 Reductive Amination of HMF
The reductive amination of HMF can produce N-substituted-5-(hydroxymethyl)-2furfuryl amines with pharmaceutical functions such as calcium antagonistic activity, cholinergic agent, antimuscarinic agent, and carcinogenesis inhibitors. Zhu
et al. used rutile titania-supported gold (Au/TiO 2 -R) catalyst to catalyze the reductive amination of HMF using Co and water as inexpensive reductant [120]. The
yield of 2,5-bis-(hydroxymethyl)furan (BHMF) reached to 93% within 2.5 h at
333 K under 20 bar CO in the presence of water/methanol (1:1). Recently, GarcíaOrtiz et al. investigated the reductive amination of HMF in the presence of Pd/C as
a catalyst using various amines and ammonia as an amine source, as well as nitrobenzene in the one-pot reaction, where N-substituted-5-(hydroxymethyl)-2-furfuryl
amines were obtained in excellent yield [124]. Furthermore, Karve et al. reported
active palladium-functionalized MOF/polymer composite (UiO-67/PpPDA/Pd) for
the reductive amination of HMF with different aliphatic and aromatic amines exhibiting electron-withdrawing or electron-donating groups [121]. A 94.5% yield for the
desired amine was obtained at 323 K under 5 MPa H 2 after 2 h in the presence of
aniline as a substrate and ethanol as a solvent (Table 6). Also, the catalyst showed
high recyclability of up to 15 cycles, which was associated with the addition of
polymer poly-para-phenylenediamine (PpPDA), which prevents the aggregation
Table 6 Summary of reductive amination of furanics over different nanocomposite catalysts
Reaction condition
Reactant Product Catalyst
Performance
Refs.
Conv.
(%)
Yield
(%)
353 K, 2 h, 2 MPa H 2 , 28% aq.
NH 3
FU
FAM
Rh/Al 2 O 3
100
92
[116]
373 K, 15 min, 3 MPa H 2 , NH 3
sol.
FU
FAM
Ru/
HZSM-5(46)
NA
75
[117]
393 K. 2 h, 0.1 MPa NH 3 and
1 MPa H 2
FU
FAM
Raney Co
100
98.9
[118]
403 K, 10 h, 5.17 MPa H 2 ,
1 mL NH 4 OH
FU
FAM
Ni/SiO 2 and Co/
SiO 2
100
90–94 [119]
363 K, 10 h, 4 MPa CO, amines
(0.5 mmol)
HMF
BHMF Au/TiO 2 -R
>99
93
[120]
323 K, 2 h, 5 MPa H 2 , aniline
(0.24 mmol)
HMF
Amine UiO-67/PpPDA/
Pd
100
94.5
[121]
373 K, 6 h, 0.1 MPa H 2 , NH 3
HMF
FAA
Ni 6 Al 1 O x
100
98
[122]
373 K, 4 h, 2 MPa H 2 , aq. NH 3
(5 mL)
HMF
AMF
Ni/SBA-15
NA
89.8
[123]
Efficient Nanocomposite Catalysts for Sustainable Production of Biofuels and…