Alcohol Amination Catalyzed by Copper Powder as a Self-Supported Catalyst

Article abstract of DOI:10.1002/cssc.201801877

Catalytic alcohol amination is a sustainable reaction for N-alkyl amine synthesis. Homogeneous and supported copper catalysts have long been studied for this reaction and have given some impressive results. In this study, copper powder is found to behave as an active catalyst for alcohol amination, giving better catalytic performance than metal-oxide-supported nanocopper catalysts. Catalyst characterization suggests that the copper powder can be considered as a self-supported nanocopper catalyst (i.e., nanocopper supported on copper particles). These results might promote the study of unsupported transition metal powders in sustainable catalytic reactions.

Full text of DOI:10.1002/cssc.201801877

Accepted Article
Title: Alcohol amination catalyzed by copper powder as a self-
supported catalyst
Authors: Yajuan Wu, Yongji Huang, Xingchao Dai, and Feng Shi
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201801877
Link to VoR: http://dx.doi.org/10.1002/cssc.201801877
A Journal of
www.chemsuschem.org

10.1002/cssc.201801877
ChemSusChem
ICATION
amination catalyzed by copper powder as a self-
ed catalyst
a,b] Yongji Huang,[a] Xingchao Dai[a,b] and Feng Shi*[a]
tic alcohol amination is a sustainable reaction for N-
thesis. In the past research, homogeneous and
r catalysts have been extensively studied and nice
ained. In this work, we’d like to show that copper
ave as an active catalyst for the alcohol amination,
c performance was better than the oxides
o-copper catalysts. Catalyst characterizations
the copper powder can be considered as the
nano-copper, i.e., nano-copper supported on
s. These results might promote the study of
ansition metal powders in sustainable catalytic
electrical conductivity, remarkable thermal conductivity, and
synergism between the metal carriers and supported nano-
metals, which would avail the hydrogen transfer process and
contribute good activity of the catalyst. Thus, it is interesting to
explore the effect of the metal supports in the bulk metal
supported nano-metal catalysts.
Herein,
a self-supported copper powder catalyst was
proposed and used to catalyze the alcohol amination reaction. In
order to compare the catalytic performance, a number of oxides
supported nano-copper catalysts were prepared by impregnation
method. The catalytic performance of the reaction was studied
and the relevant characterizations employing ICP-AES, BET,
XRD, XPS, TEM, and N2O dissociative chemisorption were
performed. Interestingly, the copper powder shows more
excellent catalytic performance than oxides supported nano-
copper catalysts. In addition, since the importance of metal
catalysis, this may provide new opportunities for metal
supported nano-metal catalysis in the further fundamental and
applied research.
n
een attracting worldwide attentions because of
n bulk and fine chemical industries for production
es, pharmaceuticals, agrochemicals, surfactants,
ly active compounds.[1] Owing to their
variety of methods for their synthesis, such
alkylation,[2] Buchwald-Hartwig[3] and
Results and Discussion
reactions,[4]
hydroamination,[5]
thylation,[6] reduction of nitriles[7] and nitro[8]
r reductive amination,[9] have been developed
tury. Compared to the above methodologies
is of N-alkyl amines, the amination of alcohol
o-called borrowing hydrogen methodology[10]
transfer methodology[5b] is highly attractive
n alcohols are readily available starting
some of them are produced on a large scale
ble resources. Besides, the amination of
rates water as the only by-product, which
cess potentially environmentally benign.[11]
omogeneous[12] and heterogeneous[13] metallic
cohol amination reaction have been developed
ogress has been achieved. As one of initially
alytic systems, copper normally suffered low
d easy deactivation.[13a] Then, the supported
s were developed and numbers of inorganic
The catalysts used in this work were commercially available or
prepared by impregnation method. The catalysts were
characterized by ICP-AES, N2 adsorption−desorption analysis,
XRD, TEM, XPS, and N2O dissociative chemisorption to reveal
their structures. According to ICP-AES analysis, the copper
loadings (wtCu) of Cu/SiO2, Cu/TiO2, Cu/γ-Al2O3, Cu/MoO3 and
Cu/WO3 were 17.6%, 15.7%, 16.7%, 19.3% and 17.9%,
respectively. N2 adsorption-desorption was used to characterize
the textual properties. For Cu and Cu(H2), the surface areas are
very low, presumably there is no pore in Cu particles. The
surface area of Cu(H2) were slightly decreased as Cu particles
Table 1. The physicochemical propertiess of the catalysts.
wtCu
SBET
Vp
Dp
DCu
[Cu]
Entry
Catalyst
(%)[a]
(m2/g)[b]
(m3/g)[b]
(Å)[b]
(%)[c]
(%)[d]
1
2
3
4
5
Cu
--
18.2
--
--
0.5
0.4
4.4
3.6
6.2
0.5
0.4
0.8
0.6
1.0
s such as Al2O3 and ZnO[15] supported copper
[14]
Cu(H2)
Cu/SiO2
Cu/TiO2
--
13.6
--
--
orted. Comparing to oxide supports, the metal
y extraordinary advantages include excellent
17.6
15.7
16.7
434.9
46.9
0.78
0.44
0.38
32.8
155.1
28.1
Cu/γ-
Al2O3
167.2
[a]
[b]
Y. Wu, Y. Huang, X. Dai and Prof. F. Shi
State Key Laboratory for Oxo Synthesis and Selective Oxidation
Lanzhou Institute of Chemical Physics
Chinese Academy of Sciences
No.18, Tianshui Middle Road, Lanzhou, 730000, China
E-mail: fshi@licp.cas.cn
Y. Wu, X. Dai
University of Chinese Academy of Sciences
No. 19A, Yuquan Road, Beijing, 100049, China
6
7
Cu/MoO3
Cu/WO3
19.3
17.9
13.2
0.06
0.08
17.5
14.8
--
--
--
--
24.15
[a] Cu mass fraction determined by IICP-AES. [b] Determined by an IQ2
automated gas sorption analyser. SBETT:Surface area; Vp: Pore volume; Dp:
Average pore diameter. [c] Cu disperssion determined by N2O dissociative
chemisorption. [d] Active Cu dispersionn is calculated by multiplying wtCu by
Supporting information for this article is given via a link at the end of
the document.
DCu
.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
Cu 2p
ted during the reduction process. The dispersion
per species in copper powder and supported Cu
measured by N2O dissociative chemisorption. As
1, the metallic copper dispersion (DCu) increased
m 0.4% of Cu(H2) to 6.2% for the Cu/γ-Al2O3
could be attributed to the dispersion effect of
The active Cu mass fraction ([Cu]) was calculated
wtCu by DCu, and enhanced gradually from 0.4%
.0% of Cu/γ-Al2O3. For Cu/MoO3 and Cu/WO3,
an not be measured accurately due to the oxide
be partially reduced during the reduction step in
e-programmed reduction. This also explains the
ons of Cu in these two catalysts.
3/2
Cu
(a)
Cu
916.5 eV
Cu
(b)
932.4 eV
+
CuO 2p
3/2
934.5 eV
Cu 2p
1/2
952.2 eVV
CuO 2p
1/2
954.5 eV
970
960
950
940
930
9900
905
910
915
920
925
930
(d)
Cu (2nd)
916.5 eV
(c)
Cu (2nd)
Cu 2p
+
3/2
932.4 eV
Cu
Cu 2p
1/2
952.2 eV
esents the XRD patterns of copper powder and
ed on different oxides. The diffraction peaks at
4.1º, 89.9º and 95.0º in the samples can be
111), Cu(200), Cu(220), Cu(311), Cu(222), which
sence of metallic Cu. As there is no obvious Cu
was observed on Cu/TiO2, Cu species are
highly dispersed on the TiO2 surface. Other
s in Figure 1d, e, f and g were attributed to
st supports (Figure S2).[16] What should be
at almost all of MoO3 was reduced to MoO2 in the
under 350 C, so the diffraction peaks at 26.3,
assignable to MoO2.[17]
905
910
915
920
925
930
970
960
950
940
930
9200
Kinetic energy (eV)
Binding Energy(eV)
Figure 2. Cu2p XPS spectra (a, c) and AAuger CuLMM spectra (b, d) of the fresh
and recycled copper powder.
Thus, combined with the results of XRD, it could be concluded
that the copper powder was oxidized to CuO and Cu2O on the
surface of Cu particles but metallic Cu in bulk phase. With
regard to Cu2p spectra of the recycled copper powder, we can
see two fitted peaks at 932.4 and 952.2 eV for Cu+ (Figure 2c, d).
It may be speculated that CuO and Cu2O were reduced to
metallic Cu by alcohols and then to catalyze the alcohol
amination reaction, which is in accordance with the results
previously reported.[18] By contrasting Figure 2 (c, d) with Figure
S3 (c, d), we could find that there is no obvious difference of
valence state between reused Cu and Cu(H2). It is speculated
that the fresh reduced and recycled catalysts were soon
oxidized to Cu+ on the surface when exposed to air, which is the
same as previously reported for Cu catalysts.[19]
l state and surface composition of the samples
by XPS. The XPS spectrum of Cu2p in Figure 3a
in peaks, and four of these can be attributed to
5 eV), Cu2+2p1/2 (954.5 eV) and two satellite
nd 962.5 eV). The two peaks at 932.4 and 952.2
ibed to Cu2p3/2 and Cu2p1/2 binding energies of
. In order to verify the chemical state of copper
peaks were collected and are shown in Figure
916.5 eV, which can be attributed to Cu+, is

: MoO : Tungsten oxide
2 
: Rutile

: Anatase

.



.

.
.
.



(g)





(f)
(e)
(d)














Figure 3. TEM images of copper powderr (a, b).
(c)
(b)
(a)
The morphologies and microstructures of the catalysts
were examined by TEM, and Figure 3 showed the images
of bulk Cu particles. Because of the large size of copper
powder particle, HR-TEM of Cu particles could not be
obtained. In Figure S4f and h, the crystal lattices of Cu(111)
can be observed clearly and thus confirms the presence of
metallic Cu. Combined with the results of XRD, Cu species
on Cu/TiO2 were crystallized and the intensity of
characteristic reflections was relatively weak, which could
40
60
80
100
2
(°)
raction patterns of catalysts Cu (a), Cu(H2) (b), Cu/SiO2 (c),
l2O3 (e), Cu/MoO3 (f) and Cu/WO3 (g).
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
the strong X-ray diffraction peak intensity of
utile. The crystal lattices of MoO2 and WO3
t not Cu (Figure S4j, l) because of the larger
of Mo and W.
To further investigate the correlation of intrinsic catalytic
activities of copper catalysts with their surface properties, their
corresponding turnover frequency (TOF[c]) values were
evaluated at a low conversion (Table 3). We could see that the
TOF[c] values of Cu and Cu(H2) are much more higher than that
of SiO2 supported copper catalyst, though the metallic copper
dispersion (D) increased dramatically from 0.4% of reduced
copper powder to 4.4% of Cu/SiO2 because of dispersion effect
of porous supports. So the high activity of copper powder should
not be attributed to its dispersity. For Cu/TiO2 and Cu/γ-Al2O3,
the yields of N-benzylaniline (Table 2) and TOFs[d] were limited
n of aniline with benzyl alcohol was chosen as a
st screening and reaction conditions optimization
t, the catalytic performance of different metal
s was investigated. A 78% conversion of aniline
tivity of N-benzylaniline was achieved when 2.5
er was used as a catalyst. The best catalytic
as attained when catalyst dosage was increased
ould be noted that there was no obvious catalytic
p when comparing the conversion and selectivity
H2), thus the hydrogen reduction procedure for
can be omitted. If oxides supported equimolar
ts, such as Cu/SiO2, Cu/TiO2, Cu/γ-Al2O3,
Cu/WO3 were employed, lower yields of N-
ere obtained. This may ascribe to the weak
een copper species and the oxides supports.
[c]
although the TOFs were relatively high. The main reason may
be that the hydrogen transfer capacity of oxides is inferior to
metals like copper.
Table 3. Catalytic performance of the cattalysts.
TOF
Conv.
Entry
Catalyst
T (h)[a]
T (h)[a]
TOF (h-1)[d]
(%)[b]
(h-1)[c]
402.2
297.8
11.5
309.1
147.5
--
creening and reaction conditions optimization.[a]
1
2
3
4
5
6
7
Cu
1
10.6
13.1
10.7
26.4
23.0
25.5
15.6
24
24
24
24
24
24
24
157.3
189.4
5.8
Cu(H2)
2
Cu/SiO2
Cu/TiO2
Cu/γ-Al2O3
Cu/MoO3
Cu/WO3
4
0.5
0.5
1
19.7
8.6
yst
Ni
Conv. (%)[b]
Yield of 3aa (%)[b]
56
59
59
46
97
99
87
78
99
32
81
69
89
80
17
8
48
50
52
36
96
99
84
75
99
4
--
Fe
2
--
--
[a] Reaction time. [b] Aniline (1 mmol), bbenzyl alcohol (1.3 mmol), catalyst (5
mol% to aniline), KOH (20 mol% to aniiline), toluene (2 mL), Ar, 160 C and
Co
determined by GC-FID using biphenyl as the internal standard
.
Pd
material. [c] TOF is calculated from thhe mole of aniline converted per mole
surface metallic Cu site at a low conveersion. [d] TOF is calculated from the
mole of aniline converted per mole surfacce metallic Cu site in 24 h.
Cu
u
With the optimized reaction conditions in hand, the scope
and generality of copper powder catalyst in the alcohol
amination reaction were explored. First, the amination of benzyl
alcohol with amine derivatives were examined. Typically, the
yield of N-benzyl aniline was 87% (Table 4, 3aa). Compared
with m-methylaniline and p-methylaniline, a lower yield was
obtained when o-methylaniline was used as a substrate because
of the steric effect (3ba). The steric effect can also be observed
when 3,5-di or 2,5-di-Me aniline was used as the starting
material, only 74% yield of N-benzyl-2,5-dimethylaniline was
obtained even the reaction time was extended to 36 h (3fa).
Excellent yields were also obtained if aniline derivatives with
u
Cu
u(H2)
iO2
TiO2
-Al2O3
26
40
80
29
9
MoO3
WO3
e
i
electron-donating groups, like MeO-, Et-, Pr-, Bu-, t-Bu-, Hex-,
were used as the starting materials. Notably, the yields of the
desired products ranged from 89% to 99% (3ga-3ma). The
reaction tolerated the presence of halogens, and 87-97% yields
of the desired products were observed when Cl-, Br-anilines
were used as starting materials (3na-3ra). The amination of
benzyl alcohol with 5-aminoindan and 1-aminon-aphthalene
were also realized and gave excellent yields (93% and 94%) to
the corresponding products (3sa, 3ta).
u
0
), benzyl alcohol (1.3 mmol), catalyst ( 5 mol% to aniline),
aniline), toluene (2 mL), Ar, 160 C, 24 h. [b] Determined by
enyl as the internal standard material. The sole by-product
eaniline 4aa. [c] No KOH was used.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
ohol amination with amines.[a]
13
98[c]
Product
Yield (%)[b]
14
15
16
17
18
19
20
87 [c]
92[c]
93[c]
87[c,d]
97[c]
93[c]
94[c]
87
81
93
84
80[c]
74[c,d]
[a] Amine (1 mmol), benzyl alcohol (1.33 mmol), catalyst ( 5 mol% to amine),
KOH (20 mol% to amine), toluene (2 mLL), 160 C, 24 h. [b] Isolated yields. [c]
The reaction temperature is 180 C. [d] TThe reaction time is 36 h.
97[c]
Subsequently, the amination reactions of different alcohols
with aniline were explored. As shown in Table 5, the benzyl
alcohols with both electron-withdrawing and electron- donating
groups on the phenyl ring underwent the alcohol amination
reaction to the corresponding products with good to excellent
yields. Benzyl alcohol with electron-donating groups, such as
89[c]
i
Me-, MeO- and Pr-, reacted smoothly affording the respective
98[c]
92[c]
93[c]
99[c]
mono-N-alkylated anilines in 81-99% yields (3ab-3ag). The
substituent at the ortho position had a substantial effect on the
reaction. For example, extended reaction time was required to
obtain high yield when o-methylbenzyl alcohol was used as a
starting material. The yields of 3ah and 3ai, for which the chloro-
group at m- and p- positions, were 93% and 81%. Further, the
heteroaromatic alcohols are also applicable to the amination
reaction (3aj-3am). In addition, the amination of aliphatic
alcohols, which are challengeable for many catalytic systems,
have attained the corresponding products in 54-80% yields
(3an-3at). Furthermore, 1, 3-benzenedimethanol (2u) led to the
desired product (3au) in good isolated yield (82%).
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
the aminaion reaction of alcohols.[a]
13
14
15
16
80[e]
71[e]
70[e]
75[c]
Product
Yield (%)[b]
98[c]
93
17
18
19
64[e]
71[e]
54[c]
97
88[c]
>99[c]
81
20
82
[a] Aniline (1 mmol), alcohol (1.3 mmol), catalyst ( 5 mol% to aniline), KOH (20
mol% to aniline), toluene (2 mL), Ar, 1800 C, 24 h. [b] Isolated yields. [c] The
reaction time is 36 h. [d] The reaction time is 48 h. [e] The reaction time
is 36 h and reaction temperature is 190 C.
To investigate the recyclability of copper powder, the used
catalyst was washed alternately with ethanol, deionized water,
methanol and acetone for 3 times. After being dried in the air at
room temperature, it was recovered and directly recharged into
the reaction tube for the next run. As shown in Figure 4, the
copper powder could be used for five catalytic cycles without
significant decline of product yield, indicating the good stability of
copper powder and thus great potential of practical application.
93
81
86[c]
96[d]
>99[d]
99[d]
Figure 4. The reusability of copper powwder. Reaction conditions: aniline (1
mmol), benzyl alcohol (1.3 mmol), Cu (55 mol% to aniline), KOH (20 mol% to
aniline), toluene (2 mL), Ar, 160 C, 9 hh. The conversions (black) and yields
(red) were determined by GC-FID with biiphenyl.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
test if the active Cu species were leached from
during the reaction, a leaching experiment was
r reaction, the mixture was filtered and the filtrate
ed by ICP-AES. Indeed, we found there was no
e. Therefore, it is clear that the copper powder
no Cu species is dissolved in the solution.
he synthesis of selected examples of
y important molecules was explored (Scheme 1).
esveratrol-derived amines are active for the
heimer’s disease,[20] has been realized with up to
her, the N-benzyl moiety has been successfully
vitamin E, D-α-tocopherol, derivative of 4-
with 72% yield.
Catalyst characterization
The contents of Cu in the catalysts were measured by inductively
coupled plasma-atomic emission spectrometry (ICP-AES), using an Iris
advantage Thermo Jarrel Ash device. XRD measurements were
conducted by a STADIP automated transmission diffractometer (STOE)
equipped with an incident beam curved germanium monochromator
selecting Cu Kα1 radiation and a 6° position sensitive detector (PSD).
The XRD patterns are scanned in the 2θ range of 10-100 °. For the data
interpretation the software WinXpow (STOE) and the database of
Powder Diffraction File (PDF) of the International Centre of Diffraction
Data (ICDD) were used. XPS were obtained using a VG ES-CALAB 210
instrument equipped with
a dual Mg/Al anode X-ray source, a
hemispherical capacitor analyzer, and a 5 keV Ar+ iron gun. The electron
binding energy was referenced to the C 1s peak at 284.8 eV. The
background pressure in the chamber was less than 10−7 Pa. The peaks
were fitted by Gaussian–Lorentzian curves after a Linear background
subtraction. For quantitative analysis, the peak area was divided by the
element-specific Scofield factor andd the transmission function of the
analyzer. TEM analysis was carried out on a Tecnai G2 F30 S-Twin
transmission electro n microscope operating at 300 KeV. NMR spectra
were measured using a Varian NMR system at 400 MHz (1H) and 100
MHz (13C). All spectra were recorded in CDCl3, and chemical shifts (δ)
were reported in ppm relative to tetramethylsilane referenced to the
residual solvent peaks. Nitrogen adsorption-desorption isotherms were
measured at 77 K using American Quantachrome iQ2 automated gas
sorption analyzer. The pore-size distribution was calculated by Barrett,
Joyner and Halenda (BJH) method from desorption isotherm. The Cu
dispersion of supported Cu catalysts was determined by N2O dissociative
chemisorption and followed H2 titration using the procedure described by
Van Der Grift et al.[22] After pretreatment in a He flow at 200 C for 30 min,
the samples were reduced in a H2 flow by heat from 50 C to 500 C at a
rate of 5 C/min. This process represented a total TPR, with reduction of
both bulk and surface Cu species. The amount of hydrogen consumption
in the first TPR was denoted as X. At the end of the first TPR, the
samples were cooled to 50 C and then purged with He flow for 20 min to
move the residual H2. After that, surface copper atoms exposed to N2O
(30 mL/min) at 50 C for 30 min. Subsequently, the samples were purged
with He flow to remove the residual N2O. At last, samples were flushed
with He to remove the oxidant and subjected to a second TPR run from
50 C to 500 C in a H2 flow at a rate of 5 C/min. During the H2-TPR
runs, the H2 consumption was tracked using a thermal conductivity
detector (TCD). Hydrogen consumption in the second TPR was denoted
as Y. The dispersion and area of surface Cu were calculated according
O
R
N
O
H
R
=
%
3va, 72%
sis of drug molecules.
s
n, we have proposed and used a simple self-
er powder catalyst system for alcohol amination
bly, the self-supported Cu catalyst presented
r catalytic performance than oxides supported
talysts. In addition, the copper powder catalyst
le recyclability and good substrate tolerance.
al conductivity, remarkable electron conductivity
with supported nano-metal particles, the metal
o-metal catalysts might provide the way of
uating and establishing simple catalyst systems
atalytic reactions.
to equations which are shown as blow
All copper atoms were reduced in the first TPR:
CuO + H Cu + H O, hydrog en consumption = X
:
al Section
2
2
as purchased from Kelong Reagent Co, Ltd (Chengdu,
her chemicals were obtained commercially and used
ification.
Reduction of surface copper atoms only:
Cu O + H
2Cu + H O, hydrogen consumption = Y
22
2
2
ration
for Cu/SiO2 preparation: 0.38 g Cu(NO3)2•3H2O, 0.5 g
nto 7 mL acetone at 25 C in a 50 mL flask under slow
min) till the acetone had evaporated, then the mixture
400 C for 4 h and reduced under hydrogen flow (10
C for 2 h. The catalysts denoted as Cu/TiO2 (P25, J&K
e/rutile = 80/20), Cu/γ-Al2O3, Cu/MoO3, Cu/WO3 were
same procedures. Cu(H2) was prepared by reducing
r under hydrogen flow at 350 C for 2 h.
The dispersion (D) was calculated as
Y
Dꢀ%ꢁ ꢂ ꢃ2 ꢄ ꢅ ꢄ 100%
X
For Copper powder and hydrogen reduced Copper powder denoted as
Cu(H2), the first TPR and N2O oxidation were regarded as pretreatment
and the consumption of H2 in the second TPR was tracked. Calibration
was made by the reduction of 16 mg of reference of CuO powder under
the same experimental conditions.[23]
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
[13] a) J. Aston, T. Peterson, J. Holowwchak, J. Am. Chem. Soc. 1934, 56,
153-154; b) A. Guyot, M. Fournieer, Bull. Soc. Chim. Fr. 1930, 47, 203-
210; c) F. Shi, M. K. Tse, S. Zhouu, M.-M. Pohl, J. Radnik, S. Hübner, K.
Jähnisch, A. Brückner, M. Beller, J. Am. Chem. Soc. 2009, 131, 1775-
1779; d) S. Nishimoto, B. Ohtanni, T. Yoshikawa, T. Kagiya, J. Am.
Chem. Soc. 1983, 105, 7180-71822.
gements
Research and Development Program of China
00), Financial supports from the NSFC
45106) and Key Research Program of Frontier
CAS (QYZDJ-SSW-SLH051) are gratefully
[14] a) A. Baiker, W. Richarz, Syntth. Commun. 1978, 8, 27-32; b) J.
Runeberg, A. Baiker, J. Kijenski, Appl. Catal. 1985, 17, 309-319; c) J.
He, K. Yamaguchi, N. Mizuno, CChhem. Lett. 2010, 39, 1182-1183; d) J.
Kijeński, P. Niedzielski, A. Baiker, Appl. Catal. 1989, 53, 107-115.
[15] T. Yamakawa, I. Tsuchiya, D. Mitsuzuka, T. Ogawa, Catal. Commun.
2004, 5, 291-295.
ohol amination • copper powder • metal-
yst • self-supported • sustainable
[16] a) L. Zhang, Y. Zhang, Y. Deng, F. Shi, Catal. Sci. Technol. 2015, 5,
3226-3234; b) X.-w. WU, J.-s. LUO, B.-z. LU, C.-h. XIE, Z.-m. PI, M.-z.
HU, T. XU, G.-g. WU, Z.-m. YU, D.-q. YI, Trans. Nonferrous Met. Soc.
China 2009, 19, 785-789.
X. Cui, Catalytic Amination for N-Alkyl Amine Synthesis,
ress, Elsevier, 2018; b) G. Guillena, D. J. Ramón, M. Yus,
2009, 110, 1611-1641.
[17] S.M.Tuominen, Powder Technol. 1981, 30, 73-76.
[18] a) Y. Wu, H. Yuan, F. Shi, ACS SSustainable Chem. Eng. 2018, 6, 1061-
1067; b) S. Pang, Y. Deng, F. Shi, Chem. Commun. 2015, 51, 9471-
9474.
ann, J. Liebigs, Ann. Chem. 1851, 78, 253-286.
o, J. R. Dunetz, Chem. Rev. 2011, 111, 2177-2250; b) Y.
schmeister, C. M. Thomas, J.-L. Renaud, Chem. Soc. Rev.
30-4145.
[19] H. Liu, Z. Huang, Z. Han, K. Ding,, H. Liu, C. Xia, J. Chen, Green Chem.
2015, 17, 4281-4290.
Fu, Y. Jiang, Y. Zhao, J. Org. Chem. 2007, 72, 672-674.
A. Tillack, N. Schwarz, M. Beller, ChemSusChem 2008, 1,
X. Shen, S. L. Buchwald, Angew. Chem. Int. Ed. 2010, 49,
K. D. Hesp, S. Tobisch, M. Stradiotto, J. Am. Chem. Soc.
13-426; d) N. R. Perl, N. D. Ide, S. Prajapati, H. H. Perfect,
D. Y. Gin, J. Am. Chem. Soc. 2009, 132, 1802-1803.
t, M. Urrutigoïty, P. Kalck, ChemCatChem 2011, 3, 1102-
O. Vieira, H. Alper, Chem. Commun. 2007, 26, 2710-2711;
d, A. M. Seayad, R. Jackstell, M. Beller, J. Am. Chem. Soc.
0311-10318.
[20] a) C. Lu, Y. Guo, J. Yan, Z. Luoo, H.-B. Luo, M. Yan, L. Huang, X. Li,
Journal of Medical Chemistry 20113, 56, 5843-5859; b) S. Elangovan, J.
Neumann, J.-B. Sortais, K. Jungee, C. Darcel, M. Beller, Nat. Commun.
2016, 7, 12641.
[21] M. Vellakkaran, K. Singh, D. Baneerjee, Acs Catal. 2017, 7, 8152-8158.
[22] C. J. G. V. D. Grift, A. F. H. Wieleers, B. P. J. Joghi, J. V. Beijnum, M. D.
Boer, M. Versluijs-Helder, J. W. GGeus, J. Catal. 1991, 131, 178-189.
[23] J. Batista, A. Pintar, D. Mandrinoo, M. Jenko, V. Martin, Appl. Catal. A:
Gen. 2001, 206, 113-124.
hou, D. Addis, S. Enthaler, K. Junge, M. Beller, Top. Catal.
9-984.
Wendt, N. Shaikh, M. Beller, Chem. Commun. 2010, 46,
bel, Y. Sun, K. Matsumura, N. Sayo, T. Saito, J. Am. Chem.
31, 11316-11317.
A. Hamid, C. L. Allen, G. W. Lamb, A. C. Maxwell, H. C.
J. A. Watson, J. M. J. Williams, J. Am. Chem. Soc. 2009,
774; b) M. H. S. A. Hamid, P. A. Slatford, J. M. J. Williams,
Catal. 2007, 349, 1555-1575.
Watson, J. M. J. Williams, Science 2010, 329, 635-636; b) S.
mm, L. Neubert, M. Zhang, H. Neumann, M. Beller,
em 2011, 3, 1853-1864.
abe, Y. Tsuji, Y. Ohsugi, Tetrahedron Lett. 1981, 22, 2667-
. Fujita, K. Yamamoto, R. Yamaguchi, Org. Lett. 2002, 4,
c) S.-C. Yang, Y.-C. Hsu, K.-H. Gan, Tetrahedron 2006, 62,
d) M. Bertoli, A. Choualeb, A. J. Lough, B. Moore, D.
G. Gusev, Organometallics 2011, 30, 3479-3482; e) M.
Y. Miyamoto, J. Ipposhi, T. Ohshima, K. Mashima, Org.
, 3371-3374; f) C. R. Reddy, E. Jithender, Tetrahedron Lett.
633-5635; g) S. Rösler, M. Ertl, T. Irrgang, R. Kempe,
m. Int. Ed. 2015, 54, 15046-15050; h) F. Shi, M. K. Tse, X.
des, D. Michalik, K. Thurow, Y. Deng, M. Beller, Angew.
d. 2009, 121, 6026-6029.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201801877
ChemSusChem
ICATION
he Table of Contents (Please choose one layout)
NICATION
Yajuan Wu, Yongji Huang, Xingchao Dai
and Feng Shi*
Page No. – Page No.
Alcohol amination catalyzed by
copper powder as a self-supported
catalyst
l amination is a sustainable reaction for N-alkyl amine synthesis. In
f-supported copper powder catalyst was defined and designed for
nation, and its catalytic performance was much better than the
ted nano-copper catalysts. This concept may provide new
or metal/porous metal supported metal catalysis for further
This article is protected by copyright. All rights reserved.