Glycerol as a Building Block for Prochiral Aminoketone, N-Formamide, and N-Methyl Amine Synthesis

Article abstract of DOI:10.1002/cssc.201600972

Prochiral aminoketones are key intermediates for the synthesis of optically active amino alcohols, and glycerol is one of the main biomass-based alcohols available in industry. In this work, glycerol was catalytically activated and purposefully converted with amines to generate highly valuable prochiral aminoketones, as well as N-formamides and N-methyl amines, over CuNiAlO_x catalyst. The catalyst structure can be anticipated as nano-Ni species on or in CuAlO_x via the formation of nano- Cu?Ni alloy particles. This concept may present a novel and valuable methodology for glycerol utilization.

Full text of DOI:10.1002/cssc.201600972

DOI: 10.1002/cssc.201600972
Communications
Very Important Paper
Glycerol as a Building Block for Prochiral Aminoketone,
N-Formamide, and N-Methyl Amine Synthesis
[a, c]
[b]
[a]
[b]
[a, b]
Xingchao Dai,
Jabor Rabeah, Hangkong Yuan, Angelika Brꢀckner,* Xinjiang Cui,
[a]
and Feng Shi*
Prochiral aminoketones are key intermediates for the synthesis
of optically active amino alcohols, and glycerol is one of the
main biomass-based alcohols available in industry. In this work,
glycerol was catalytically activated and purposefully converted
with amines to generate highly valuable prochiral amino-
ketones, as well as N-formamides and N-methyl amines, over
maceutical substances are known to contain amino alcohol
[3]
moieties. In addition to biotechnological methods, a wide va-
riety of methodologies has been developed for the reduction
[4]
of prochiral aminoketones with various catalyst systems.
However, prochiral aminoketones are commonly synthesized
by complicated reactions such as a-amino acid reduction, alco-
hol oxidation, addition of organometallic reagents, and re-oxi-
CuNiAlO catalyst. The catalyst structure can be anticipated as
x
[3,5]
nano-Ni species on or in CuAlO via the formation of nano-
dation. Recently, it was revealed that glycerol can behave as
a suitable alkylation reagent with amines, catalyzed by
x
CuꢀNi alloy particles. This concept may present a novel and
[6]
[7]
valuable methodology for glycerol utilization.
copper or heteropolyacid-based catalysts. However, the re-
action conditions are rigorous (190–2908C) and the generality
of the catalyst system is still not good. It would be highly
desirable if an efficient and sustainable methodology could be
developed for the synthesis of prochiral aminoketones.
The catalytic conversion of biomass-based molecules has been
the subject of intense research efforts in the past decade,. Eth-
anol, glycol, glycerol, and furan derivatives are typical biobased
The development of alcohol amination reactions that allow
the environmentally compatible generation of amine deriva-
tives from simple and readily available starting materials is at
the forefront of fine chemical synthesis, and it offers great po-
tential for industrial development. In this context, great prog-
ress has been made in the search for efficient catalytic process-
es for reactions of various amines with primary and even sec-
[
1]
feedstocks. Among these compounds, glycerol is a potentially
important biorefinery feedstock that is available as a byproduct
in the production of biodiesel. In 2014, the annual output of
biodiesel reached 29.1 million tons and about 3 million tons of
glycerol was co-produced! However, it is still a big challenge
for chemists to efficiently transform biomass-based glycerol
into value-added molecules. In fact, the highly functionalized
nature of glycerol provides a unique opportunity to transform
it into a variety of molecules, such as dihydroxyacetone, meso-
xalic acid, 1,3-propanediol, 1,3-dichloropropanol, glyceryl
[8]
ondary alcohols using versatile catalysts. Based on our con-
[9]
tinuing studies in alcohol amination, we found that CuNiMOx
(M=Fe or Al) showed good performance in glycerol activation
and alcohol amination reactions. Therefore, we supposed that
glycerol could be employed as a building block for the synthe-
sis of prochiral aminoketones, N-formamides, and N-methyl
[
2]
ethers, glycerol carbonate, glyceryl esters, or syngas. Howev-
er, almost all of these processes comprise the oxidation, reduc-
tion, halogenation, or etherification of glycerol itself. A more
valuable stategy would be to use glycerol directly as a building
block for the synthesis of value-added compounds. Unfortu-
nately, to date, reports on this topic have been scarce.
amines (Scheme 1) with a heterogeneous CuNiAlO catalyst. In
x
this way, a novel and economic methodology could be devel-
oped for the application of glycerol as a building block in the
synthesis of nitrogen-containing fine chemicals.
Amino alcohols are important compounds in nature and in
pharmaceutical chemistry, and a large number of active phar-
A series of NiꢀCu catalysts were prepared by a co-precipita-
tion method, in which combined solutions of Cu(NO ) ,
3
2
Ni(NO ) and/or Al(NO ) were precipitated with an alkali base
3
2
3 3
(
see the Supporting Information), characterized by different an-
[a] X. Dai, H. Yuan, Dr. X. Cui, Prof. Dr. F. Shi
State Key Laboratory for Oxo Synthesis and Selective Oxidation Center for
Green Chemistry and Catalysis
Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences
No.18, Tianshui Middle Road, Lanzhou, 730000 (China)
E-mail: fshi@licp.cas.cn
alytical techniques and tested for prochiral amino synthesis by
using the reaction of morpholine with glycerol as a model
(
Table 1). Clearly the highest catalytic performance was ob-
served with CuNiAlO catalysts (Table 1, entries 1–4). Upon ad-
x
dition of 10% K CO , the conversion of morpholine was 91%
[
b] Dr. J. Rabeah, Prof. Dr. A. Brꢀckner, Dr. X. Cui
Leibniz-Institut fꢀr Katalyse e. V. an der Universitꢁt Rostock (LIKAT)
Albert-Einstein-Strasse 29a, 18059 Rostock (Germany)
E-mail: angelika.brueckner@catalysis.de
2
3
and the selectivity to N-acetonyl morpholine reached 99%.
Therefore, the influence of base addition on the reaction was
explored. No desired product was detectable without the Cu-
[
c] X. Dai
NiAlO catalyst (Table 1, entry 5). The presence of base was also
x
University of Chinese Academy of Sciences
important, because only 41% selectivity was maintained under
base-free conditions (Table 1, entry 6). Using other bases, such
No. 19 A, Yuquanlu, Beijing, 100049 (China)
Supporting information for this article can be found under http://
dx.doi.org/10.1002/cssc.201600972.
ChemSusChem 2016, 9, 1 – 7
1
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

Communications
XRD characterization, and the crystal lattice planes
Ni(200), Ni(111), and Cu(111) can be observed (see
the Supporting Information, Figure S2).
Moreover, a Cu and Ni K-edge EXAFS study was
performed on samples CuNiO , CuAlO , NiAlO , and
x
x
x
CuNiAlO to further elucidate the structure of the cat-
x
alysts (Figures 2 and 3). Based on a comparison with
standard spectra, CuꢀO coordination can be exclud-
ed from CuNiO and CuNiAlO but a small peak for
x
x
CuꢀO was detected for CuAlO . However, the CuꢀCu
x
and CuꢀNi spectra overlap with each other so they
cannot be defined. Furthermore, the Ni K-edge
EXAFS spectra was also measured. The NiꢀO peaks
were very weak in all of the samples, which implies
that the major Ni species may exist in the form of
Scheme 1. One-pot synthesis of a-aminoketones, formamide, and N-methyl amine with
amine and glycerol.
metallic Ni, in the agreement with the results of XRD. More-
[
a]
Table 1. Catalyst screening and reaction conditions optimization
over, the spectra of CuꢀNi alloy and CuNiO are almost the
x
same, which indicates the formation of CuꢀNi alloy species,
[
b]
[b]
Entry
Catalyst
CuNiO
Base
T [h]
Conv. [%]
Sel. [%]
1
2
3
4
5
6
7
8
9
x
K
K
K
2
CO
2
CO
2
CO
3
3
3
12
12
12
12
6
6
6
6
6
58
20
54
91
3
80
71
34
64
44
99
99
99
99
0
41
95
97
99
97
NiAlO
x
CuAlO
x
CuNiAlO
–
x
K
2
CO
CO
3
K
–
2
3
CuNiAlO
CuNiAlO
CuNiAlO
CuNiAlO
CuNiAlO
x
x
KOH
NaOH
x
x
x
K
2
CO
3
10
Na
2
CO
3
6
[
(
a] Reaction conditions: morpholine (1 mmol), glycerol (5 mmol), catalyst
50 mg), base (10 mol%), 1,4-dioxane (2 mL), Ar atmosphere, 1508C,
6–12 h; [b] determined by GC-MS.
as KOH, NaOH, and Na CO , led to low conversions and/or low
2
3
selectivities (Table 1, entries 7–10).
To explore the correlation of structure and activity, the pre-
pared catalysts were extensively characterized. According to
the inductively coupled plasma atomic emission spectroscopy
Figure 1. XRD diffraction patterns of prepared catalysts: a) CuNiOx;
b) CuAlO ; NiAlO ; d) CuNiAlO .
x x x
(ICP-AES) analysis of CuNiOx (Cu/Ni=1:2), CuAlOx (Cu/Al=
1
:2.7), NiAlO (Ni/Al=2:2.7), and CuNiAlO (Cu/Ni/Al=1:2:2.7)
x
x
catalysts, the Cu loadings were 38.4%, 16.1% and 11.6%, and
the Ni loadings were 72.4%, 15.0% and 21.9%, respectively
(see the Supporting Information, Table S1). The BET surface
areas of catalysts CuNiO , CuAlO , NiAlO and CuNiAlO were
x
x
x
x
2
ꢀ1
9
.6, 126.5, 168.2 and 170.4 m g (see the Supporting Informa-
tion, Table S1 and Figure S1).
The powder XRD patterns are showed in Figure 1. In the
CuAlO catalyst, Cu(111), Cu(200), Cu(220), and Cu(311) reflec-
x
tions indicate the presence of metallic Cu. Typical metallic Ni
reflections of Ni(111), Ni(200), Ni(220), Ni(311), and Ni(222) are
detected in the CuNiO and NiAlO catalysts. However, these
x
x
peaks are a bit wider in the CuNiAlO catalyst, probably due to
x
the contribution of CuꢀNi alloy to the XRD reflections. Addi-
tionally, some AlO (311) (2q=37.08) and AlO (111) (2q=66.08)
x
x
signals are also detected in catalysts CuAlO , NiAlO , and
x
x
2
Figure 2. Fourier transform (FT) of Cu K-edge EXAFS: a) Cu foil; b) Cu O;
CuNiAlO . The HR-TEM image confirms the observations from
c) CuO; d) CuꢀNi alloy; e) CuNiO
x x x
; f) CuAlO ; g) CuNiAlO .
x
&
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
2
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communications
Figure 4. EPR spectra of CuNiAlO
tures.
x
catalyst measured at different tempera-
Figure 3. Fourier transform (FT) of Ni K-edge EXAFS: a) Ni foil; b) Ni
c) CuꢀNi alloy; d) CuNiO ; e) NiAlO ; f) CuNiAlO
2 3
O ;
x
x
x
.
100 K (see the Supporting Information, Figure S3b) showed
and no typical CuꢀNi peak was observed in CuNiAlO . There-
a very broad and strong anisotropic signal at g=3.662. On rais-
ing the measuring temperature to 450 K, the signal became
less anisotropic, the g value shifted to the high-field region,
x
fore, we can ascertain the major Ni species in the CuNiAlO
x
sample might be metallic Ni. Also, the spectra of NiAlO are
x
similar to that of CuNiAlO . In light of these results, we
x
can determine that the major Ni species should be CuꢀNi
[
a]
Table 2. Results of N-Acetonyl amine synthesis of different amines.
alloy in CuNiO but metallic Ni in NiAlO and CuNiAlO .
x
x
x
Meanwhile, the Cu species in all samples should be metal-
Entry Products
Yield
[%]
Entry Products
Yield
[%]
[
b]
[b]
lic Cu, except for a small quantity of CuO in CuAlO . In ad-
x
dition, some of the Cu in CuNiO adopted the form of
x
94
CuꢀNi alloy analogue. Similar observations could be infer-
red from the XAFS spectra of Cu and Ni (see the Support-
ing Information, Figures S5 and S6) and the results of
curve-fitting analysis suggested that the coordination
[c]
[e]
1
2
3
91
93
10
77
70
86
[d]]
[
e]
79
11
numbers in the active catalyst CuNiAlO were 0.8 and 2.7
x
78
12
13
for CuꢀO and NiꢀO, respectively (see the Supporting In-
formation, Figures S7 and S8 and Table S2).
To obtain greater insight into the nature of the active
sites in this catalytic reaction, EPR spectra of the fresh cat-
alysts (Figure 4 and Figure S3 in the Supporting Informa-
tion) were measured at different temperatures (T=100–
4
5
78
79
70
80
14
4
50 K). The EPR spectrum of CuAlO (see the Supporting
x
Information, Figure S3a) exhibits an axial EPR signal at g
?
6
7
81
82
91
15
16
17
74
17
62
=
2.035 and g =2.346 with hyperfine structure A =
j
j
j
j
65,63
II
9
133 G ( Cu , d , I=3/2) as evident from the 2nd deriva-
tive of the EPR spectrum (see the Supporting Information,
[f]
[f]
II
Figure S4), indicating the presence of Cu ion single site.
This was also supported by the EXAFS spectra of CuAlOx
[
e]
8
catalysts, which showed a small characteristic peak of Cuꢀ
II
O (Figure 3 f). The formation of the Cu ion is attributed to
the oxidation of copper upon contact with air which
cannot be totally excluded. Additionally, the EPR spectrum
exhibits a broad signal at g=2.20 due to the dipole–
dipole and weak exchange magnetic interaction between
[f]
9
85
18
73
[
(
a] Reaction conditions (unless otherwise stated): amine (1 mmol), glycerol
5 mmol), CuNiAlO (50 mg), K CO (10 mol%), 1,4-dioxane (2 mL), Ar atmos-
phere, 1508C (heating temperature), 24 h (entries 1–11) or 36 h (entries 12–16);
[b] yield of isolated product; [c] c was used at the 2nd run; [d] catalyst was used
at the 3rd run; [e] 0.5 mmol amine was used; [f] results obtained by GC-MS
without correction.
x
2
3
II
[10]
II
Cu ions. The intensity of the Cu signal decreased on
raising the measuring temperature without changing its g
value, indicating the paramagnetic nature of the CuAlOx
catalyst. The EPR spectrum of NiAlO catalyst measured at
x
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
3
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

Communications
and its line width became narrow, indicating the presence of
Ni ferromagnetic particles. The increasingly strong anisotropic
magnetic behavior with temperature suggests an inhomoge-
neous distribution of Ni particle sizes and/or the presence of
non-spherical particles, which is in agreement with the result
of TEM (see the Supporting Information, Figure S2). The EPR
4-yl)propane were applied (Table 2, entries 8–11). The CuNiAlOx
catalyst is also active for the N-acetonyl amine synthesis with
normal secondary amine as starting material. Typically, the iso-
lated desired products could be obtained in 70–82% yield
when dipropyl amine, dibutyl amine, dioctyl amine, and diben-
zyl amine were applied as the starting materials (Table 2, en-
tries 12–15). Unfortunately, only 17% yield of the desired prod-
uct was obtained if aliphatic and aromatic primary amines,
such as n-heptyl amine, aniline, and p-methyl aniline, were em-
ployed (Table 2, entries 16–18), indicating that this catalyst is
not good for the synthesis of N-acetonyl amines with primary
amines.
spectrum of CuNiO shows a similar spectral trend to that ob-
x
served for NiAlO catalyst (Figure S3c). However, the ferromag-
x
netic signal is much stronger and less anisotropic (Figure S3b
vs. S3c). This could be attributed to the lowered specific sur-
2
ꢀ1
face area of CuNiO (9.6 m g ), which leads to increased size
x
of the Ni ferromagnetic particles. The contribution of CuO to
the EPR signal can be ruled out since it is well known that CuO
aggregates do not give rise to any EPR signal, owing to the
Finally, the reusability of CuNiAlO catalyst was tested for the
x
reaction of morpholine with glycerol (Table 2, entry 1). After
each reaction, the catalyst was recovered by simple centri-
fugation, washed, and reused without further treatment. The
catalyst was recycled for 3 runs without obvious deactivation.
Glycerol can behave as an efficient carbonyl resource for
formamide synthesis with the addition of suitable amount of
oxygen, because formic acid can be produced through oxida-
II
[11]
very strong spin interaction between Cu ions. Moreover, no
II
evidence for the existence of Cu single sites could be ob-
tained from the EPR measurements. It should be noted that
CuOꢀNiO oxide materials are characterized by their paramag-
[
12]
netic nature, whereas our CuNiO catalyst has a characteristic
x
EPR signal owing to the formation of Ni-based ferromagnetic
particles. This was also supported by XRD, TEM and EXAFS in-
vestigations.
[15]
tive CꢀC bond cleavage of glycerol. The formic acid would
quickly react with amine to generate N-formyl amine. We next
undertook catalyst screening and reaction conditions optimiza-
tion for this reaction (Table 3). Good to excellent results were
obtained when cyclic and linear secondary amines were ap-
plied as starting materials, and the yields of the isolated de-
sired N-formyl amine reached 81% (Table 3, entries 1–8). Mod-
From the temperature-dependent EPR spectrum of the most
active catalyst CuNiAlO (Figure 4), it can be seen that there is
x
II
no contribution of Cu ions to the EPR signal. Moreover, the
magnetic anisotropy of the EPR signal of the CuNiAlO catalyst
x
(signal shape and line width) is more pronounced than in
CuNiO but less than in NiAlO (Figure 4 and Figure S3b,c
x
x
in the Supporting Information). Naghash et al. reported
that incorporation of copper into Ni lattice leads to an in-
[a]
Table 3. Results of N-formyl amine synthesis with amines and glycerol.
[
13]
crease in its lattice parameter. Moreover, it is well known
that the larger the aggregates, the narrower the resonance
line and the lower the temperature change of the g
[
14]
Entry Products
Yield
Entry Products
Yield
value
This indicates that incorporation of Cu into NiAlOx
[b]
[b]
[
%]
[%]
catalyst leads to more homogeneous distribution of the Ni
particle size and shape in the CuNiAlO catalyst, probably
x
1
2
3
70
81
63
7
8
9
71
41
56
due to the formation small CuꢀNi alloy nanoparticles in
comparison with that of CuNiO catalyst.
x
Based on the combined evaluation of spectroscopic
data discussed above, the structure of the active catalyst
CuNiAlO can be anticipated as nanoscopic Ni species on
x
or in CuAlO , which is in good agreement with the obser-
x
vations from EXAFS and XRD analysis.
Next, the scope and limitations of the CuNiAlO catalyst
x
were explored with the reaction of different amines with
glycerol (Table 2). Firstly, cyclic secondary amines were
tested and N-acetonyl morpholine was obtained in 94%
yield (isolated product; Table 2, entry 1). Good results can
also be obtained for piperidine derivatives with different
substituents as starting materials, giving the desired prod-
ucts in 78–85% yield (Table 2, entries 2–5). Piperazine de-
rivatives were tested, giving yields of 81% and 82% with
N-methyl and N-ethyl piperazine, respectively, as the start-
ing materials (Table 2, entries 6 and 7). Interestingly, N,N-di-
acetonyl products could also be generated from dicyclic
amines. For example, up to 91% yields were achieved
when piperazine, 2-methyl piperazine and 1,3-di(piperidin-
4
60
10
47
[
c]
c]
5
6
49
58
11
12
45
45
[
[
a] Reaction conditions (unless otherwise stated): amine (1 mmol), glycerol
(0.5 mmol), CuNiAlO (50 mg), 1,4-dioxane (2 mL), O (0.5 MPa), 1508C (heating
temperature), 3 h; [b] yield of isolated product; [c] 0.5 mmol starting materials
were used.
x
2
&
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
4
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Communications
1
3
Scheme 2. a-Aminoketone, formamide, and N-methyl amine syntheses with amine and C glycerol. Results were determined by GC-MS.
erate yields were generated when aliphatic primary amines
were used as the starting materials (Table 3, entries 9–12).
The incorporation of Cu and Ni into one catalyst was essential
to realize these transformations. This concept may promote
the catalytic transformation of bio-based glycerol into value-
added molecules by design of heterogeneous catalysts.
[
9e,16]
Glycerol is a potential hydrogen source,
which can be
[16]
used for the catalytic reduction of carbonyl compounds. It
was therefore possible for us to synthesize N-methyl amine fol-
lowing the generation of N-formyl amine. To our delight, the
N-methyl amine was successfully produced in a mixed reaction
medium (water+1,4-dioxane), with the addition of suitable
amount of glycerol (Table 4). Good to excellent results were
obtained for N-formyl amine synthesis when cyclic and linear
secondary amines were applied as starting materials. Notably,
up to 80% yield was achieved when dipropylamine was ap-
plied as the starting material.
Acknowledgements
The National Natural Science Foundation of China (21303228)
and Youth Innovation Promotion Association CAS are gratefully
acknowledged. We thank Prof. Dr. Lirong Zheng at the Institute
of High Energy Physics, Chinese Academy of Sciences for helping
us to perform the EXAFS analysis.
13
Finally the reaction of morpholine and C glycerol was per-
formed to check whether the acetonyl, formyl, and methyl
groups were derived from glycerol (Scheme 2). The results of
GC-MS analysis clearly proved this conjecture, establishing that
glycerol can be a functional building block for the synthesis of
value-added molecules.
Keywords: alkylation · amination · heterogeneous catalysis ·
glycerol · formylation
[
1] a) A. J. Straathof, Chem. Rev. 2014, 114, 1871–1908; b) T. J. Morgan, R.
Kandiyoti, Chem. Rev. 2014, 114, 1547–1607; c) M. Besson, P. Gallezot, C.
Pinel, Chem. Rev. 2014, 114, 1827–1870; d) A. Corma, S. Iborra, A. Velty,
Chem. Rev. 2007, 107, 2411–2502.
In summary, glycerol was catalytically activated and reacted
directionally with primary and secondary amines to generate
highly valuable prochiral aminoketones, as well as N-forma-
mide and N-methyl amine, with excellent yields over a simple
[
[
[
2] T. Werpy, G. Petersen, Top Value Added Chemical from Biomass: Volu-
me I—Results of Screening for Potential Candidates from Sugars and Syn-
thesis Gas, U.S. D.O.E. report, 2004.
3] a) P. Etayo, A. Vidal-Ferran, Chem. Soc. Rev. 2013, 42, 728–754; b) M. M.
Midland, Chem. Rev. 1989, 89, 1553–1561; c) F. D. Klingler, Acc. Chem.
Res. 2007, 40, 1367–1376.
CuNiAlO catalyst. To our knowledge, this is the first time that
x
glycerol has been reported to behave as a versatile building
block to selectively synthesize different valuable molecules.
4] a) R. Noyori, I. Tomino, Y. Tanimoto, M. Nishizawa, J. Am. Chem. Soc.
1
984, 106, 6709–6716; b) R. Noyori, I. Tomino, M. Yamada, M. Nishiza-
wa, J. Am. Chem. Soc. 1984, 106, 6717–6725; c) E. J. Corey, R. K. Bakshi,
S. Shibata, J. Am. Chem. Soc. 1987, 109, 5551–5553; d) K. Mashima, K.
Kusano, N. Sate, Y. Matsumura, K. Nozaki, H. Kumobayashi, N. Sayo, Y.
Hori, T. Ishizaki, S. Akutagawa, H. Takaya, J. Org. Chem. 1994, 59, 3064–
[
a]
Table 4. N-methyl amine synthesis with amine and glycerol.
3076; e) T. Ohkuma, D. Ishii, H. Takeno, R. Noyori, J. Am. Chem. Soc.
2
000, 122, 6510–6511; f) M. Studer, H. U. Blaser, C. Exner, Adv. Synth.
Catal. 2003, 345, 45–65; g) P. He, H. Zheng, X. Liu, X. Lian, L. Lin, X.
Feng, Chem. Eur. J. 2014, 20, 13482–13486; h) Y. Li, S. Yu, X. Wu, J. Xiao,
W. Shen, Z. Dong, J. Gao, J. Am. Chem. Soc. 2014, 136, 4031–4039; i) J.
Guo, J. Chen, Z. Lu, Chem. Commun. 2015, 51, 5725–5727.
Amine
Yield [%]
Amine Yield [%]
62
Amine
Yield [%]
61
4
4
5
5
[
[
[
[
5] A. Alcꢂntara, V. Pace, A. Cabrera, M. Fernandez, J. Sinisterra, Synthesis
2
010, 2010, 3545–3555.
[
b]
31
80
6] M. Watanabe, G. Tateno, Y. Mimura (Kao Corporation, Tokyo),
JP2010120886, 2010.
7] M. Safariamin, S. Paul, K. Moonen, D. Ulrichts, F. Dumeignil, B. Katryniok,
Catal. Sci. Technol. 2016, 6, 2129–2135.
8] a) C. L. Allen, J. M. Williams, Chem. Soc. Rev. 2011, 40, 3405–3415;
b) T. D. Nixon, M. K. Whittlesey, J. M. Williams, Dalton Trans. 2009, 753–
[
a] Reaction conditions (unless otherwise stated): amine (1 mmol), glycer-
ol (10 mmol), CuNiAlO (50 mg), mixed solvent (2.5 mL; 2 mL deionized
water and 0.5 mL 1,4-dioxane), O (0.5 MPa), 1508C (heating temperature),
h, yields determined by GC-FID using butanol as an external standard;
b] t=8 h.
x
2
4
[
762; c) S. Bꢃhn, S. Imm, L. Neubert, M. Zhang, H. Neumann, M. Beller,
ChemCatChem 2011, 3, 1853–1864; d) M. Zhang, S. Imm, S. Bahn, H.
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
5
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ

Communications
Neumann, M. Beller, Angew. Chem. Int. Ed. 2011, 50, 11197–11201;
Angew. Chem. 2011, 123, 11393–11397; e) G. E. Dobereiner, R. H. Crab-
tree, Chem. Rev. 2010, 110, 681–703; f) G. Guillena, D. J. Ramon, M. Yus,
Chem. Rev. 2010, 110, 1611–1641.
9] a) H. Yang, X. Cui, X. Dai, Y. Deng, F. Shi, Nat. Commun. 2015, 6, 6478;
b) X. Cui, X. Dai, Y. Deng, F. Shi, Chem. Sci. 2014, 5, 649–655; c) M. Pera-
Titus, F. Shi, ChemSusChem 2014, 7, 720–722; d) X. Cui, C. Zhang, F. Shi,
Y. Deng, Chem. Commun. 2012, 48, 9391–9393; e) X. Dai, X. Cui, H.
Yuan, Y. Deng, F. Shi, RSC Adv. 2015, 5, 7970–7975; f) X. Cui, X. Dai, Y.
Deng, F. Shi, Chem. Eur. J. 2013, 19, 3665–3675.
[12] H.-K. Kim, W. Honda, B.-S. Kim, I.-S. Kim, J. Mater. Sci. 2013, 48, 1111–
1116.
[13] A. R. Naghash, T. H. Etsell, S. Xu, Chem. Mater. 2006, 18, 2480–2488.
[14] E. G. Derouane, A. J. Simoens, J. C. Vꢄdrine, Chem. Phys. Lett. 1977, 52,
549–553.
[
[15] J. Zhang, M. Sun, X. Liu, Y. Han, Catal. Today 2014, 233, 77–82.
[
16] M. B. Gawande, A. K. Rathi, P. S. Branco, I. D. Nogueira, A. Velhinho, J. J.
Shrikhande, U. U. Indulkar, R. V. Jayaram, C. A. A. Ghumman, N. Bundale-
ski, O. M. N. D. Teodoro, Chem. Eur. J. 2012, 18, 12628–12632.
[
10] B. J. Hathaway, D. E. Billing, Coord. Chem. Rev. 1970, 5, 143–207.
11] P. Simon, J. M. Bassat, S. B. Oseroff, Z. Fisk, S. W. Cheong, A. Wattiaux, S.
Schultz, Phys. Rev. B 1993, 48, 4216–4218.
Received: July 19, 2016
Revised: August 29, 2016
Published online on && &&, 0000
[
&
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
6
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

COMMUNICATIONS
X. Dai, J. Rabeah, H. Yuan, A. Brꢀckner,*
X. Cui, F. Shi*
&& – &&
Glycerol as a Building Block for
Prochiral Aminoketone, N-Formamide,
and N-Methyl Amine Synthesis
Amines to an end: The catalytic trans-
formation of glycerol into value-added
molecules is an important field in sus-
tainable chemistry. In this work, glycerol
was activated and reacted directionally
with primary and secondary amines to
generate highly valuable prochiral ami-
noketones, N-formamide, and N-methyl
amine with excellent yields over
a simple CuNiAlO catalyst.
x
ChemSusChem 2016, 9, 1 – 7
www.chemsuschem.org
7
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ