Unique Chemoselective Hydrogenation using a Palladium Catalyst Immobilized on Ceramic

Article abstract of DOI:10.1002/cctc.201500193

A heterogeneous palladium catalyst supported on a ceramic (5 % Pd/ceramic) was developed. The catalyst exhibited a specific chemoselectivity for hydrogenation that has never been achieved by other palladium-catalyzed methods. Either aliphatic or aromatic N-Cbz groups could be deprotected to the corresponding free-amines, while the hydrogenolysis of benzyl esters and ethers did not proceed. Furthermore, aryl chlorides and epoxides were tolerant under the Pd/ceramic-catalyzed hydrogenation conditions. 5 % Pd/ceramic could be reused without any loss of catalyst activity, as no palladium leaching was detected in the reaction media.

Full text of DOI:10.1002/cctc.201500193

DOI: 10.1002/cctc.201500193
Full Papers
Unique Chemoselective Hydrogenation using a Palladium
Catalyst Immobilized on Ceramic
[
a]
[a]
[a]
[b]
Yasunari Monguchi,* Takahisa Marumoto, Tomohiro Ichikawa, Yutaka Miyake,
[c]
[d]
[e]
[a]
Yoshiyuki Nagae, Michiyuki Yoshida, Yasunori Oumi, Yoshinari Sawama, and
[
a]
Hironao Sajiki*
A heterogeneous palladium catalyst supported on a ceramic
5% Pd/ceramic) was developed. The catalyst exhibited a spe-
esters and ethers did not proceed. Furthermore, aryl chlorides
and epoxides were tolerant under the Pd/ceramic-catalyzed
hydrogenation conditions. 5% Pd/ceramic could be reused
without any loss of catalyst activity, as no palladium leaching
was detected in the reaction media.
(
cific chemoselectivity for hydrogenation that has never been
achieved by other palladium-catalyzed methods. Either aliphat-
ic or aromatic N-Cbz groups could be deprotected to the cor-
responding free-amines, while the hydrogenolysis of benzyl
Introduction
[
24a]
Clay, which is a raw material of ceramics, is one of most typical
materials as the supports for the heterogeneous palladium cat-
alysts. A variety of palladium catalysts supported on clay, such
action efficiency for the generation of benzene
and styre-
[
24b,c]
ne
from cyclohexane and ethylbenzene, respectively, by
the ceramic-supported or -coated palladium-catalyzed dehy-
drogenation could be enhanced, owing to the efficient remov-
al of the generated hydrogen gas from the reaction system.
However, the application of such palladium on ceramics as the
[
1,2]
[3]
[4]
as bentonite,
vermiculite, pillared clay, montmorillon-
[
5–16]
[17–19]
[20–22]
ite,
hydrotalcite,
and hydroxyapatite,
has been
prepared and used for the hydrogenation; e.g., semihydroge-
[4,6–13,17]
[25,26]
nation of alkynes to the corresponding alkenes.
Al-
hydrogenation catalysts has hardly been studied.
though the use of ceramics combined with palladium species
has also been studied, such functional ingredients are mainly
We recently developed an effective method for the immobi-
[
27]
lization of palladium(0) metal on various materials, including
[
23,24]
[27f,g]
[27h–j]
utilized as hydrogen-permeable membrane materials
for
molecular sieves (MS),
boron nitride (BN),
and a syn-
[24]
the dehydrogenation of saturated compounds, thus, the re-
thetic adsorbent DIAION HP20 (HP20), just by their immersion
[
27k–m]
in a MeOH solution of palladium acetate.
Furthermore,
the activity of such palladium catalysts for the hydrogenation
was found to depend on the kind or nature of the support ma-
terials. The support-specific chemoselectivities could be ap-
plied as chemoselective hydrogenation methods. For example,
[
a] Dr. Y. Monguchi, T. Marumoto, T. Ichikawa, Dr. Y. Sawama, Prof. Dr. H. Sajiki
Laboratory of Organic Chemistry
Gifu Pharmaceutical University
1
-25-4 Daigaku-nishi, Gifu 501-1196 (Japan)
E-mail: monguchi@gifu-pu.ac.jp
sajiki@gifu-pu.ac.jp
[
27f,g]
palladium on MS5A (Pd/MS5A)
and palladium on BN (Pd/
[
27h–j]
[
b] Y. Miyake
Wako Pure Chemical Industries, Ltd.
663 Matoba, Kawagoe, Saitama 350-1101 (Japan)
c] Y. Nagae
Brightceram
-25 Zendaiji, Kani, Gifu 509-0204 (Japan)
BN)
could catalyze only alkynes, alkenes, and azides in the
presence of other reducible functionalities, such as nitro,
benzyl ester, etc., while palladium on HP20 (Pd/HP20) could be
used for the reduction of a wide variety of reducible functiona-
1
[
[
27k,m]
lities.
1
The ceramic industry has been thriving in the Tokai district
in Japan, including Gifu Prefecture, where our university is lo-
cated. We expected that the utilization of a ceramic as a sup-
port for a hydrogenation catalyst could connect chemistry to
our traditional and regional industry, as the development of
chemoselective hydrogenation methods or catalysts is in
demand for new effective synthetic routes in organic chemis-
try.
[
d] Dr. M. Yoshida
Department of Chemistry and Biomolecular Science
Faculty of Engineering
Gifu University
1
-1 Yanagido, Gifu 501-1193 (Japan)
[
e] Dr. Y. Oumi
Instrumental Analysis
Life Science Research Center
Gifu University
1
-1 Yanagido, Gifu 501-1193 (Japan)
In this paper, we describe the development of a ceramic-
supported palladium catalyst and its general application to the
hydrogenation of a variety of reducible functionalities with
a unique chemoselectivity.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201500193.
This publication is part of a Special Issue on Palladium Catalysis. To view
the complete issue, visit:
http://onlinelibrary.wiley.com/doi/10.1002/cctc.v7.14/issuetoc
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Results and Discussion
Ceramic tiles for supports of an immobilized palladium catalyst
were prepared according to the general methods in ceramic
engineering by calcining a mixture of alumina, silica, silicon
carbide, and several clays including potter’s clay kibushi clay,
and chamotte. Table 1 shows the composition of the prepared
Table 1. Composition of the ceramic by SQX analysis [mol%].
SiO
5.4
2
Al
32.8
2
O
3
CaO
25.9
MgO
2.57
K
1.54
2
O
Na
0.55
2
O
TiO
0.12
2
3
Fe
2
O
3
Cl
0.05
SO
0.59
3
P
0.02
2
O
5
SrO
0.01
ZrO
2
0.01
0
.37
ceramic, which was determined by Scan Quant X (SQX) analy-
sis, a semiquantitative analysis of elements in materials without
any standardized references, using a wavelength-dispersive X-
ray fluorescence spectrometer. The major components are Si
and Al, and the mole ratio of Si to Al is approximately 1:1. A
relatively large amount of Ca was also contained in the ceram-
ic with a 1:1.4 mole ratio of Ca to Al. These ratios are quite
similar to those of MS 5 Š, although it is low in Ca (mole ratio
of Ca/Al<1/2). As the ceramic is composed of a wide variety
of elements, which might affect the catalyst activity, besides Si,
Al, and Ca compared to MS 5 Š, we expected the ceramic-sup-
ported palladium catalyst to exhibit a unique chemoselectivity
Figure 1. XRD spectra of a) ceramic and b) 5% Pd/ceramic. !: the (111) face
of palladium species.
[
28]
in hydrogenation.
The palladium on ceramic was prepared as follows: ceramic
tiles were crushed and powdered using a mortar and pestle,
then stirred in a palladium acetate solution in MeOH at RT for
6
days (Scheme 1). The white powdered ceramic tiles turned
Scheme 1. Preparation of palladium on ceramic.
Figure 2. TEM image of 5% Pd/ceramic.
grayish, and the supernatant solution became colorless during
the preparation, indicating that the palladium should be em-
bedded on the ceramic as palladium(0). The palladium-sup-
ported ceramic was collected on a filter paper (1 mm), washed
The 5% Pd/ceramic-catalyzed hydrogenation of various sub-
strates possessing reducible functionalities in a molecule was
investigated (Table 2). Alkyne (Entries 1, 12, 15, 16, 31, 35, and
37), alkene (Entries 2, 13, 14, 17–19, 22, 24–30, 32, 33, and 36),
and azido (Entries 3, 4, and 20) functionalities were readily hy-
drogenated to the corresponding alkanes and amines. When
an azido group was present with the nitro-functionalized sub-
strate, the reduction of the nitro group to an amino group was
impeded presumably due to the catalyst poison effect of the
quickly generated azido-derived amino group based on its co-
ordination to the palladium metal, and heating at 508C was re-
quired for the completion of the reaction (Entries 4 and 5); the
with H O and MeOH, and dried at RT in vacuo for 2 days. The
2
palladium content of the catalyst was determined to be 5 wt%
[
27]
by the atomic absorption analysis of the filtrate and wash.
The X-ray diffraction (XRD) spectroscopy revealed the exis-
tence of crystalline palladium in the 5% Pd/ceramic, thus
a peak at 2q=ca. 408 for the (111) face of palladium species
emerges in the complex diffraction peaks derived from ceramic
support (Figure 1). The crystalline size of the palladium parti-
cles is estimated to be approximately 10 nm from the transmis-
sion electron microscopy (TEM) of the 5% Pd/ceramic, and sev-
eral particles aggregate to form a cluster (Figure 2)
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Table 2. The 5% Pd/ceramic-catalyzed hydrogenation of various reducible
Table 2. (Continued)
functionalities.
Entry Substrate
P
T
t
Product
Yield
[%]
[atm] [8C] [h]
[
b,d]
2
2
2
3
4
5
1
RT 24 recovery
100
100
99
Entry Substrate
P
T
t
Product
Yield
[%]
[atm] [8C] [h]
[a,d]
1
1
1
1
RT
RT
6
3
[
a]
1
2
1
1
RT
RT
6
6
98
[
[
[
a]
[a]
100
a]
2
2
6
7
RT 24
100
100
[a]
3
1
RT
9
97
a,d]
RT
RT
3
6
4
1
RT 24
–
[a]
2
8
1
1
100
–
35:65
29
RT 24
[a]
5
1
50 12
100
70:30
[
a]
3
0
3
1
RT 24
RT 12
92
86
[
[
[
a]
b]
a]
[a]
6
7
8
9
1
1
5
1
RT
5
100
100
100
12
31
[
[
a]
a]
3
3
3
2
3
4
1
1
1
RT
3
99
100
100
RT 24 recovery
50 24
RT 24
RT 12
[e]
[
a]
35
36
37
1
1
1
RT 12
82
93
[
[
[
c]
c]
a]
RT 24
[a]
RT
3
[
a]
RT 12
100
1
0
5
1
50 24
11
[
a] The substrate was completely consumed to afford the corresponding
product with 100% conversion. The turnover number of the 5% Pd/ceramic
is 100. [b] Yield of the recovered starting material. [c] Ratio of consumed sub-
11
RT
9
100
3
strate. [d] The reaction was performed in CD OD, owing to the volatile
[
[
[
a]
nature of the starting material and/or products, and the conversion was de-
termined by H NMR measurement. [e] 10% Pd/C was used as the catalyst.
1
1
1
2
3
4
1
1
1
RT 24
RT 24
RT 24
98
100
100
1
a]
a,d]
nitro group could be smoothly reduced when 4-nitrobenzyl al-
cohol, which does not possess amino groups, was employed
as a substrate (Entry 6). In that case, no hydrogenolysis (deoxy-
genation) of the coexisting benzyl alcohol to the correspond-
ing toluene derivative took place. The tolerance of the benzyl
alcohol under the 5% Pd/ceramic-catalyzed hydrogenation
conditions might be estimated by the catalyst suppression
effect of the amino group initially formed from the nitro
group. However, 5% Pd/ceramic was found to be not active
for the hydrogenolysis of benzyl alcohols, which possess no
amino or other possible strong catalyst poisonous functionali-
ties, was also intact under the present hydrogenation condi-
tions (Entry 7). The aromatic aldehyde and ketone were less re-
active; pressurized hydrogen with heat (5 atm, 508C) was re-
quired for completion of the hydrogenation of the aromatic al-
dehyde to afford the corresponding benzyl alcohols without
any formation of deoxygenated toluene (Entry 8), while the hy-
1
5
1
RT 24
–
72:28
[
[
[
a,d]
a]
16
17
18
1
1
1
50 24
100
97
RT
RT
6
6
a]
99
[
[
a]
a]
1
2
9
0
1
1
RT
6
99
85
RT 12
[
[
b]
2
2
1
2
1
1
RT 24 recovery
RT
100
100
a,d]
7
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drogenation of the aromatic ketone hardly proceeded even
under the same conditions (Entries 9 and 10). The aromatic car-
bonyl group of 4-nitroacetophenone was intact at RT under
ramic could successfully and clearly build a new framework in
the figure; it can catalyze the hydrogenolysis of aliphatic and
aromatic N-Cbz groups and aromatic aldehydes, while benzyl
esters and ethers, epoxides, and aryl chlorides could never be
reduced.
1
atm H atmospheric conditions presumably due to the cata-
2
lyst poisonous effect of the initially generated amino group
Entries 9 vs. 11). The hydrogenolysis of the N-benzyloxycar-
(
The reuse test of 5% Pd/ceramic was investigated for the
hydrogenation of diphenylacetylene (Table 3). 5% Pd/ceramic
bonyl (Cbz)-protected aliphatic and aromatic amines could be
achieved (Entries 12–16), although the deprotection to n-pro-
pylamine as an aliphatic primary amine was slightly sluggish
(
Entries 15 and 16). On the other hand, the benzyl protecting
Table 3. Reuse test of 5% Pd/ceramic.
group of both aliphatic and aromatic carboxylic acids could
not be removed under an H atmosphere, and the selective hy-
2
drogenation of the coexisting alkene and azido functionalities
proceeded (Entries 17–20). Aromatic and aliphatic benzyl
ethers (Entries 21 and 22) and aromatic chlorides (Entries 23
and 24) were also tolerant, and the coexisting alkenes could
be selectively hydrogenated (Entries 22 and 24). Epoxides were
stable for the hydrogenolysis using 5% Pd/ceramic as a catalyst
Run
1st
95
2nd
3rd
4th
5th
Recovered catalyst [%]
Yield [%]
98
99
80
100
77
99
76
96
100
(
Entries 25–28). The catalyst activity toward silyl ethers, which
have been recognized to be relatively unstable protecting
groups of the alcohols toward the hydrogenation using MeOH
was recovered by filtration using a 1 mm filter paper after the
hydrogenation reaction for 6 h, and the reaction progress was
[
29]
1
as a solvent, was next investigated. The relatively labile trie-
thylsilyl (TES)-protecting cinnamyl alcohol underwent a partial
confirmed by a H NMR analysis after concentration of the fil-
trate. As a result, 5% Pd/ceramic could be reused for at least
5 runs without any loss of its catalyst activity. Furthermore, the
inductively coupled plasma-atomic emission spectroscopy of
the filtrate (first run) indicated no palladium leaching from the
catalyst within its detectable limit (<1 ppm). Although the
gradual decrease in the amount of the recovered catalyst was
observed with each run, it would be attributed to the insuffi-
cient and difficult recovery of the catalyst from the filter paper,
owing to the further fine powdering during the continuous
magnetic stirring.
hydrogenolysis at RT under atmospheric H (Entry 29), and the
2
complete deprotection was achieved by increasing the hydro-
gen pressure to 3 atm (Entry 30). On the other hand, the hy-
drogenolysis of the TES ether with a coexisting alkyne func-
tionality never proceeded (Entry 31). More stable silyl protect-
ing groups, such as the tert-butyldimethylsilyl (TBS) and triiso-
propylsilyl (TIPS) groups, were totally tolerant (Entries 32, 33,
and 35–37), while the cinnamyl TBS ether was readily depro-
tected together with the hydrogenation of the coexisting
alkene moiety using 10% Pd/C as the catalyst (Entry 34).
The XRD and TEM analyses of recovered 5% Pd/ceramic
after the hydrogenation of diphenylacetylene indicate no sig-
nificant change in the morphology of palladium particles (Fig-
ure 1b vs 4 and Figure 2 vs. 5). These results support that the
5% Pd/ceramic maintains its activity for reuse in the hydroge-
nation.
Figure 3 shows the activity of the palladium catalysts, which
were developed in our laboratory, except for Pd/C, for the hy-
drogenation of various reducible functionalities. The reducible
functionalities inside the frameworks can be reduced by hydro-
genation using the corresponding palladium catalysts. Pd/ce-
Figure 3. Activity of palladium catalysts for hydrogenation of various reduci-
ble functionalities.
Figure 4. XRD spectra of recovered 5% Pd/ceramic after the hydrogenation
of diphenylacetylene. !: the (111) face of palladium species.
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(
2 wt%). The mixture underwent press molding, drying, and calcin-
ing at 12508C for 10 h to produce the ceramic.
Preparation of 5% Pd/ceramic
The ceramic was powdered using a mortar and pestle. To a solution
of Pd(OAc) [527 mg, 2.35 mmol, (250 mg, palladium quantity)] in
2
MeOH (50 mL) was added the powdered ceramic (5.00 g), and the
mixture was stirred at RT under an Ar atmosphere for 6 days. The
gray powder was collected on a Kiriyama funnel (1 mm, filter
paper), washed with MeOH (20 mL) and H O (20 mL), and dried
2
under reduced pressure for 1 day to give Pd/ceramic (5.24 g). The
palladium amount in the filtrate was determined to be 2.75 mg by
atomic absorption analysis, which means that the palladium
amount of the Pd/ceramic was 4.7% [(250–2.75)/5240”100].
Figure 5. TEM image of recovered 5% Pd/ceramic after the hydrogenation
of diphenylacetylene.
Conclusions
General procedure for 5% Pd/ceramic-catalyzed hydrogena-
tion
We developed a novel heterogeneous palladium catalyst sup-
ported on a ceramic (5% Pd/ceramic), which showed a unique
chemoselectivity for the hydrogenation of various reducible
functionalities. The 5% Pd/ceramic could be successfully pre-
pared just by stirring the powdered ceramic, which was pro-
duced by a general ceramic engineering procedure, in a solu-
tion of palladium acetate in MeOH; palladium(II) ions were em-
bedded on the ceramic and then reduced to palladium(0)
metal by MeOH. Although alkyne, alkene, azide, nitro, N-Cbz,
and aromatic aldehyde functionalities could be reduced under
the hydrogenation conditions, aryl chlorides, epoxides, benzyl
esters, benzyl ethers, benzyl alcohols, and silyl ethers were tol-
erant toward the 5% Pd/ceramic-catalyzed hydrogenation. Al-
though the reason for this novel and unique chemoselectivity
is not currently clear, it will be clarified by further investigation
of the effect of the clay components and conditions of the ce-
ramic preparation, such as calcining temperature and time.
The catalyst would be useful as a new tool for organic synthe-
sis, owing to its selectivity, non-palladium-residual property,
and reusability.
A mixture of the substrate (0.500 mmol) and 5% Pd/ceramic
(
10.6 mg, 5.00 mmol, 1 mol%) in MeOH (1 mL) was stirred under an
H2 atmosphere (balloon) at room temperature. After a specific
time, the mixture was filtered through a Millipore membrane filter
(
0.45 mm), the catalyst was washed with Et O (10 mL), then the fil-
2
trate and wash were combined and concentrated in vacuo to give
the corresponding reduced product. If the reaction was not com-
pleted, the temperature was raised to 40 or 508C. If the reaction
was still incomplete, the H
pressure was increased to 3, 5 or
2
1
9
atm. All the products were known, and the H NMR spectral data
of the products were identical to those in the literature (see the
Supporting Information).
Reuse test of 5% Pd/ceramic
Ten test tubes were prepared, then diphenylacetylene (44.6 mg,
0
.250 mmol), 5% Pd/ceramic (5.3 mg, 2.50 mmol, 1 mol%), and
MeOH (1 mL) were placed in each test tube. The mixture in each
test tube was stirred under an H atmosphere (balloon) at room
2
temperature for 6 h, then all the mixtures were filtered using a Kir-
iyama funnel (1 mm filter paper). The catalyst on the filter paper
was washed with Et O (10 mL), and the filtrate was concentrated in
vacuo to give 1,2-diphenylethane in 100% yield (455 mg,
2
Experimental Section
2
.50 mmol). The recovered catalyst was dried at room temperature
General
under reduced pressure for 12 h, then weighed [50.1 mg, 95%,
50.1Ä(5.3”10)”100]. The reaction for the second run was per-
formed in the same manner as the first run, but using seven test
tubes [total substrate amount, 312 mg (44.6 mg”7), 1.75 mmol
(0.250 mmol”7), total catalyst amount, 37.1 mg (5.3 mg”7)]. 1,2-
Diphenylethane was obtained in 99% yield (315 mg, 1.73 mmol),
and the catalyst was recovered in 98% yield (36.3 mg). The reac-
tions for the third to fifth runs were also performed in the same
manner as the first run except for the number of used test tubes.
The results are summarized in the Supporting Information.
Pd(OAc) was obtained from the N.E. Chemcat Co. (Tokyo, Japan).
The H NMR spectra were measured by a JEOL JMN AL-400 spec-
2
1
trometer (400 MHz) using CDCl or CD OD as the solvent. Chemical
3
3
shifts (d) were expressed in ppm and internally referenced
0.00 ppm for tetramethylsilane/CDCl or 3.30 ppm for CD OD). The
(
3
3
SQX analysis was performed at the Gifu Prefectural Ceramics Re-
search Institute (Gifu, Japan) by using a Rigaku ZSX100e sequential
X-ray fluorescence spectrometer (Tokyo, Japan). BET, XRD, and TEM
studies were performed in Gifu University by using a Belsorp-mini
II (MicrotracBEL Corp., Osaka, Japan), D8 Advance (Bruker Corp.,
Billerica, USA), and JEM-2100 (JEOL Ltd., Tokyo, Japan), respectively.
Leaching test of 5% Pd/ceramic
A mixture of diphenylacetylene (2.06 g, 11.6 mmol), 5% Pd/ceramic
Preparation of ceramic
(
250 mg, 116 mmol, 1 mol%), and MeOH (46 mL) was stirred under
The ceramic was prepared according to the general and standard
ceramic engineering procedure. To a 5:1 mixture of potter’s clay
and kibushi clay were added alumina (12 wt%), silica (5 wt%), sili-
con carbide (5 wt%), chamotte (15 wt%), and shirasu balloon
an H atmosphere (balloon) at room temperature for 6 h, then the
2
mixture was filtered using a Millipore membrane filter (0.2 mm) and
the catalyst on the filter was washed with MeOH (10 mL”3). The
combined filtrate and wash were transferred to a 100 mL volumet-
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ric flask, and MeOH was added to 100 mL of total volume. The re-
sidual palladium concentration was measured using a Shimadzu
ICP8000, and no palladium was detected within the limits of the
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We thank the N.E. Chemcat Corporation for the ICP-AES measure-
ment of the eluted palladium species from the 5% Pd/ceramic
into the reaction mixture. Y.M. thanks the Saijiro Endo Memorial
Foundation for the partial financial support of this study.
[
[
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Keywords: ceramic
·
chemoselectivity
·
heterogeneous
catalysis · hydrogenation · palladium
[26] Some examples for the use of ceramic materials as catalyst supports:
a) M. A. Keane, J. Mater. Sci. 2003, 38, 4661–4675; b) H. Friedrich, P. E.
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Received: February 27, 2015
Revised: April 6, 2015
Published online on May 28, 2015
ChemCatChem 2015, 7, 2155 – 2160
www.chemcatchem.org
2160
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