Gold nanoparticle-catalyzed environmentally benign deoxygenation of epoxides to alkenes

Article abstract of DOI:10.3390/molecules16108209

We have developed a highly efficient and green catalytic deoxygenation of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite [HT: Mg₆Al₂CO₃(OH)₁₆] (Au/HT) with alcohols, CO/H₂O or H₂ as the reducing reagent. Various epoxides were selectively converted to the corresponding alkenes. Among the novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture and reused with retention of its catalytic activity and selectivity. The high catalytic performance of Au/HT was attributed to the selective formation of Au-hydride species by the cooperative effect between Au NPs and HT.

Full text of DOI:10.3390/molecules16108209

Molecules 2011, 16, 8209-8227; doi:10.3390/molecules16108209
OPEN ACCESS
molecules
ISSN 1420-3049
www.mdpi.com/journal/molecules
Article
Gold Nanoparticle-Catalyzed Environmentally Benign
Deoxygenation of Epoxides to Alkenes
Akifumi Noujima 1, Takato Mitsudome 1, Tomoo Mizugaki 1, Koichiro Jitsukawa 1 and
Kiyotomi Kaneda 1,2,
*
1
Department of Materials Engineering Science, Graduate School of Engineering Science,
Osaka University, 1-3, Machikaneyama, Toyonaka, Osaka 560-8531, Japan
Research Center for Solar Energy Chemistry Osaka University, 1-3, Machikaneyama, Toyonaka,
Osaka 560-8531, Japan
2
* Author to whom correspondence should be addressed; E-Mail: kaneda@cheng.es.osaka-u.ac.jp;
Tel.: +81-6-6850-6260; Fax: +81-6-6850-6260.
Received: 5 September 2011; in revised form: 16 September 2011 / Accepted: 21 September 2011 /
Published: 28 September 2011
Abstract: We have developed a highly efficient and green catalytic deoxygenation
of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite
[HT: Mg6Al2CO3(OH)16] (Au/HT) with alcohols, CO/H2O or H2 as the reducing reagent.
Various epoxides were selectively converted to the corresponding alkenes. Among the
novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the
deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture
and reused with retention of its catalytic activity and selectivity. The high catalytic
performance of Au/HT was attributed to the selective formation of Au-hydride species by
the cooperative effect between Au NPs and HT.
Keywords: gold nanoparticle; hydrotalcite; deoxygenation; epoxide; alkene
1. Introduction
The chemoselective reduction of organic compounds is one of the most fundamental reactions in
organic chemistry. Among these reductive reactions, the deoxygenation of epoxides into alkenes
(Scheme 1) has attracted much attention in both organic synthesis and biological chemistry where, for

Molecules 2011, 16
8210
example, it occurs in the protection-deprotection cycle of carbon-carbon double bonds [1-3] and in the
production of vitamin K in the human body [4,5].
Scheme 1. Deoxygenation of epoxides to the corresponding alkenes.
Reductant
O
R2
R2
R1
R1
Generally, stoichiometric deoxygenations of epoxides have been conducted using expensive
and/or toxic reagents such as low valent metals [6-13], iodides [14-17], phosphines [18-20], and silane
compounds [21-23]. These reagents are often employed in excess, resulting in the production of large
amounts of waste. To date, catalytic deoxygenations using Re complexes with triphenylphosphine [24-26],
a Fe complex with NaBH4 [27], and a Co complex with Na [28] have been reported, but these
homogeneous catalytic systems have suffered from tedious work-up procedures, air- and moisture-
sensitive reaction conditions, low atom efficiency and low catalytic activities. Therefore, the
development of highly efficient and environmentally benign catalytic deoxygenation of epoxides is
still a challenging issue.
Gold nanoparticles (Au NPs) have received much attention in the catalysis field due to their unique
and high oxidation ability in various reactions such as oxidation of CO [29] and alcohols [30,31], and
epoxidation of alkenes [32,33]. On the other hand, the reduction ability of the Au NP catalysts has not
yet been widely studied despite their remarkable activities [34,35]. We have focused on exploring the
novel catalytic reactions of Au NPs, and found that supported Au NPs showed unprecedented
reduction activities in the deoxygenation of epoxides [36-38], N-oxides, sulfoxides, and amides [39].
In this account, we review our recent progress on the unique catalysis of Au NPs supported on
hydrotalcite [HT: Mg6Al2CO3(OH)16] (Au/HT) for deoxygenation of epoxides to the corresponding
alkenes using alcohols [36] or CO/H2O [37] as reductant (Scheme 2). A wide range of epoxides were
deoxygenated to the corresponding alkenes with over 99% selectivities. The C=C bonds of the
products were not hydrogenated at all. After the reaction, the solid Au/HT catalyst could be easily
separated and reused without loss of its activity or selectivity. Furthermore, Au/HT was successfully
applicable to an ideal deoxygenation, i.e., the H2-mediated deoxygenation of epoxides where only
water is formed as a by-product [38].
Scheme 2. Deoxygenation of epoxides catalyzed by Au/HT.
Au/HT
O
R2
R2
R1
R1
alcohols, CO/H2O or H2
2. Results and Discussion
2.1. Characterization of Au/HT
Au/HT was prepared by the deposition precipitation method (see Experimental). From atomic force
microscopy (AFM) and transmission electron microscopy (TEM) analyses, the mean diameter (d) of
Au NPs on the surface of HT was 2.7 nm with a standard deviation (σ) of 0.7 nm (Figure 1).

Molecules 2011, 16
Figure 1. AFM (a); TEM (b) and size distribution (c) of Au NPs on HT.
(a) (b) (c)
8211
2.2. Deoxygenation of Epoxides to Alkenes
2.2.1. Au/HT-Catalyzed Deoxygenation of Epoxides Using Alcohols as a Reductant
Recently, we have found that Au/HT could catalyze the highly efficient aerobic oxidation of
alcohols [40] and the lactonization of diols [41]. These results allowed us to predict that if epoxides
could be employed as hydrogen acceptors in place of molecular oxygen under the alcohol oxidation
conditions, a green catalytic deoxygenation of epoxides with alcohols could be developed (Scheme 3) [36].
Scheme 3. The oxidation of alcohols using O2 vs. deoxygenation of epoxides using alcohols.
OH
R'
O
R
R
R'
H2O
1/2 O2
O
R2
R2
+ H2O
R1
R1
Epoxides
Alkenes
O
OH
R'
R
R'
R
To demonstrate the above hypothesis, we carried out the deoxygenation of trans-stilbene oxide (1)
using Au/HT with 2-propanol in toluene as the solvent at 110 °C under Ar atmosphere for 4 h. 1 was
successfully deoxygenated to give the corresponding alkene trans-stilbene (2) in quantitative yield.
Notably, no by-products such as 1,2-diphenylethanol or 1,2-diphenylethane resulting from the
hydrogenation of 1 or 2 were formed (Table 1, Entry 1). During the deoxygenation of 1, the amounts
of acetone and water generated were almost equivalent to that of 2. Among the alcohols tested,
1-phenylethanol and benzyl alcohol could also function as reductants (Entries 2 and 3), while the use
of an aliphatic primary alcohol such as 1-octanol resulted in lower yield (Entry 4). Next, the effects of
inorganic supports of Au NPs were investigated. Au NPs on basic supports of Al2O3 and MgO
afforded good to moderate yields of 2 (Entries 5 and 6), whereas non-basic supports like TiO2 and
SiO2 were not effective (Entries 7 and 8). Other Au compounds like HAuCl4, Au2O3 and bulk Au

Molecules 2011, 16
8212
metal did not promote the deoxygenation (Entries 9–11). These results indicate that the combination of
Au NPs and a basic support is necessary to achieve the high catalytic activity for the deoxygenation.
Table 1. Deoxygenation of trans-stilbene oxide a.
O
Catalyst
Ph
Ph
Ph
Ph
toluene, alcohol (10 equiv.), 110 °C, Ar, 4 h
1
2
1 mmol
Entry
Catalyst
Au/HT
Au/HT
Au/HT
Au/HT
Au/Al2O3
Au/MgO
Au/TiO2
Au/SiO2
HAuCl4
Au2O3
Alcohol
2-propanol
1-phenylethanol
benzyl alcohol
1-octanol
Conv. b (%)
Sel. b (%)
>99
>99
>99
>99
>99
>99
>99
>99
-
1
2
3
4
5
6
7
8
9
99
99
91
37
60
43
19
5
2-propanol
2-propanol
2-propanol
2-propanol
2-propanol
2-propanol
2-propanol
<1
<1
0
10
11
-
-
bulk Au metal
a Au cat. (0.45 mol%), toluene (5 mL), alcohol (10 mmol); b Determined by HPLC using an internal
standard technique.
Other metal NPs on HT were examined for the deoxygenation of 1 (Figure 2). Among the catalysts
tested, Ag/HT also showed excellent catalytic activity for deoxygenation, while other metal NPs did
not function as catalysts.
Figure 2. Deoxygenation of trans-stilbene oxide using HT-supported various metal NPs.
O
M/HT (M: 0.45 mol%)
Ph
Ph
Ph
Ph
toluene (5 mL), 2-PrOH (10 equiv.),
110 °C, Ar, 4 h
2
1
To investigate the possibility of the leaching of active metal species from Au/HT into the reaction
mixtures, Au/HT was filtered from the reaction mixture at 50% conversion of 1, and treatment of the

Molecules 2011, 16
8213
filtrate with additional stirring under similar conditions did not give any product. Furthermore,
inductively coupled plasma atomic emission spectral (ICP-AES) analysis revealed no Au species in the
filtrates (detection limit: 0.1 ppm). These results clearly proved that no leaching occurred and the
deoxygenation proceeded on the Au NPs on HT.
The outstanding catalytic activity of Au NPs encouraged us to investigate the scope of epoxides in
the deoxygenation (Table 2). Various epoxides were efficiently converted into the corresponding
alkenes with over 99% selectivity. Both aromatic and aliphatic epoxides could be deoxygenated.
Epoxides having ether and hydroxyl groups were also successfully employed as substrates (Entries 9
and 16). Notably, the reducible C=O bonds of epoxyketones were tolerated in the deoxygenation
(Entries 14 and 15). cis-Stilbene oxide and cis-2,3-epoxyoctane gave (Z)/(E)-alkene stereoisomers. The
selectivities for cis-alkenes were 60% and 50%, respectively (Entries 4 and 13).
Table 2. Deoxygenation of various epoxides using Au/HT a.
O
Au/HT (Au: 0.45 mol%)
R2
R1
toluene (5 mL), 2-PrOH (0.6 mL), 110 oC, Ar
R1
R2
Entry
Substrate
Product
Time (h) Conv. b (%)
Yield b (%)
1
4
4
4
99
99
97
99
O
2 c
3 d
99
97
O
4
4
99
97 (E/Z) = 2/3
O
O
5
6 e
7
4
6
6
98
>99
96
98
98
92
O
O
8
9
6
6
94
93
89
91
90
89
s
F
F
O
O
O
O
10
24
O
11
24
4
87
87
97
O
12 e
>99

Molecules 2011, 16
8214
Table 2. Cont.
Product
Time (h) Conv. b (%)
Entry
Substrate
Yield b (%)
O
13 f
12
81
77 (E/Z) = 1/1
O
O
14 f
15 f
16 f
17
24
24
6
88
99
93
72
85
94
91
68
O
O
O
O
OH
OH
O
O
24
a Reaction conditions: Au/HT (0.1 g), substrate (1 mmol), Ar; b Determined by GC or HPLC using
an internal standard technique; c Reuse 1; d Reuse 2; e 80 °C; f Substrate (0.3 mmol), catalyst (0.2 g).
After the deoxygenation of 1, the solid Au/HT catalyst could be easily separated from the reaction
mixtures and reused with retention of its performance (Entries 2 and 3). TEM images showed that the
Au NPs on HT after reuse were similar to fresh Au/HT in average diameter and size distribution and
no aggregation of the used Au NPs was observed (Figure 3).
Figure 3. TEM image and size distribution of Au NPs of Au/HT after reuse experiments.
Atomic-scale analysis using Au L-edge EXAFS of Au/HT showed that the intensity of the FT peak
derived from the Au-Au shell at 2.8 Å was not changed, supporting the observation that the Au NPs
after reuse were of the same size as the originals. These results are consistent with the high durability
of Au/HT in the recycling experiments.
Au/HT was also applicable in a preparative scale reaction (Scheme 4). Thus, the deoxygenation of
20 mmol of 1 successfully proceeded to afford 2 with 95% isolated yield in 2-propanol as solvent after
72 h, where the TON and TOF reached 20,000 and 270 h−1, respectively. These values are three orders
of magnitude greater than those of previously reported catalytic systems such as Tp’ReO3-PPh3
(TON = 19) [24], polystyrene-supported Re-PPh3 (TON = 18, TOF = 12 h−1) [26], CH3ReO3-PPh3

Molecules 2011, 16
8215
(TON = 8, TOF = 0.4) [25], [Fe4S4(SC6H5)4]3−-NaBH4 (TON = 4, TOF = 1 h−1) [27], and Co complex-
Na (Hg) (TON = 5, TOF = 0.8 h−1) [28].
Scheme 4. Preparative deoxygenation of trans-stilbene oxide using Au/HT.
Au/HT (0.0045 mol%)
O
2-PrOH (20 mL), 150 oC, Ar, 72 h
1
2
(3.2 g, 95 % yield)
20 mmol (3.9 g)
TON = 20000, TOF = 270 h-1
In separate experiments, the use of d-benzhydrol [C6H5CD(OD)C6H5] as a reductant for the
deoxygenation of 1 afforded 2 and D2O with all hydrogen atoms in the alkene product retained. From
both these results and the positive effect of basic supports as shown in Table 1 (Entries 1, 5 and 6), we
propose the following mechanism as shown in Scheme 5.
Scheme 5. A plausible reaction mechanism for the Au/HT-catalyzed deoxygenation of an
epoxide through the cooperation of the Au NPs with basic sites (BS) of HT.
A basic site (denoted as BS) of HT abstracts the H+ from the hydroxyl group of the alcohol to
promote the formation of an Au-alcoholate species which subsequently forms an Au-hydride species
and the corresponding carbonyl compound through β-hydride elimination [42]. The Au-hydride
species and H+ attack an epoxide, providing an alkene and H2O. The distinguished deoxygenation
activities of Au NPs from those of other metal NPs should be attributed to the reactivity toward an
epoxides (III→I) because the other metal NPs of Cu, Ru, Pd and Rh, which can form metal-hydride
species from the reaction with the alcohol (I→III), do not deoxygenate the epoxide.

Molecules 2011, 16
8216
2.2.2. Deoxygenation of Epoxides with CO/H2O
We have previously reported that Rh carbonyl species can deoxygenate nitro compounds in the
presence of amines as bases under water-gas shift reaction conditions (CO + H2O → CO2 + H2) [43].
In this reaction, CO and H2O react with the Rh carbonyl species and an amine to form a Rh-hydride
species that is active for the reduction of nitro compounds. The formation of the Rh-hydride species in
cooperation with amines under water-gas shift reaction conditions inspired us to develop an alternative
catalytic deoxygenation system using Au/HT. Namely, we proposed that an active Au-hydride species
for the deoxygenation of epoxides can be formed through the cooperative effect of HT as a base under
water-gas shift reaction conditions (Scheme 6). Thus, the attack of H2O on the basic sites of HT to CO
adsorbed on Au NPs generates [Au-COOH]−, followed by the elimination of CO2 to give the
Au-hydride species and H+, which then act in concert to deoxygenate epoxides to alkenes [37].
Scheme 6. Concerted effects between HT and Au NPs for the formation of Au-H species
(BS represents base site of HT).
O
C
O
C
HO
C
CO2
R
O
H2O
H+
H
-
H+
BS
HT
H+
BS
HT
Au
OH
H2O
BS
BS
HT
Au
Au
Au
Au
BS
HT
O
HT
R
Based on the above hypothesis, we carried out the deoxygenation of styrene oxide (1a) under water-
gas shift reaction conditions in the presence of Au/HT. Styrene (2a) was quantitatively obtained as the
sole product under atmospheric pressure CO in water at room temperature (Table 3, Entry 1). Various
epoxides tested in the Au/HT-2-propanol system were also reactive under water-gas shift conditions
(Table 4). Compared with the Au/HT-2-propanol system, this Au/HT-CO/H2O system can promote the
deoxygenation of epoxides under mild and convenient reaction conditions, e.g., at room temperature,
1 atm of CO, and in the absence of organic solvents.
Table 3. Deoxygenation of styrene oxide using CO/H2O a.
O
Au Catalyst
Ph
Ph
water (5 mL), CO (1 atm), 27 oC, 6 h
2a
1a
0.5 mmol
Entry
Catalyst
Au/HT
Au/HT
Au/HT
Au/Al2O3
Au/MgO
Yield b (%)
Sel. b (%)
>99
1
2 c
3 d
4
>99
>99
97
79
36
>99
>99
>99
>99
5
6
Au/TiO2
Au/TiO2 + Na2CO3
Au/SiO2
18
57
>99
>99
>99
7 e
8
3
a
b
Reaction conditions: catalyst (M: 0.9 mol%); water; Determined by GC using an internal
standard technique; c Reuse 1; d Reuse 2; e Na2CO3 (1.5 mmol) was added.

Molecules 2011, 16
Table 4. Deoxygenation of various epoxides with CO/H2O using Au/HT a.
8217
O
Au/HT
R2
water (5 mL), CO (1 atm), 27 oC
R1
R1
R2
Entry
Substrate
Product
Time (h) Yield b (%) Sel. b (%)
O
1
6
>99 (94)
90 (85)
99 (94)
90 (85)
96 (90)
>99
>99
>99
>99
96
O
2
3
4
5
12
12
16
16
O
F
F
O
O
OH
OH
O
O
O
6
7
24
24
90 (83)
>99
>99
O
75 (69)
a
b
Reaction conditions: Substrate (0.5 mmol), Au/HT (0.1 g, Au: 0.9 mol%); Determined by GC
c
using an internal standard technique. Values in parentheses are isolated yields; Cinnamaldehyde
was formed as a byproduct.
Scheme 7. Solvent effect on the deoxygenation of epoxides.
O
Au/HT (Au: 0.9 mol%)
solvent (5 mL), water (0.1 mL)
27 oC, CO (1 atm), 6 h
1a
2a
Solvent Yield (%)
0.5 mmol
water
toluene
THF
>99
73
60
6
DMA
O
Au/HT (Au: 0.9 mol%)
OH
OH
O
+
solvent (5 mL), water (0.1 mL)
27 oC, CO (1 atm), 16 h
1b
0.5 mmol
2b
by-product
Sel. (%)
Solvent Yield (%)
water
toluene
THF
96
82
36
96
82
36

Molecules 2011, 16
8218
The solvent effect on the deoxygenation is shown in Scheme 7. Notably, water was found to
provide the highest yield among all the solvents tested despite the water-insoluble nature of 1a. In the
case of the epoxy alcohol 2,3-epoxy-3-phenyl-1-propanol (1b), the highest yield and selectivity of
cinnamyl alcohol (2b) were obtained in water. After the deoxygenation of 1a, 2a was easily extracted
from the reaction mixture by n-hexane and the recovered aqueous phase containing solid Au/HT could
be recycled with no decrease in catalytic activity (Table 3, Entries 2 and 3).
Figure 4. FTIR spectra of (a) Au/HT and (b) after CO/H2O adsorption at 298 K.
2163 2126 (CO)
0.05
1640 (CO2)
(b)
1750
(a)
2300
2000
1700
1400
Wavenumber / cm−1
To gain more insight into the deoxygenation under the water-gas shift conditions, the following
control experments were carried out. When the reaction was conducted in the absence of 1a under
otherwise identical conditions, H2 was not detected. The use of D2O in place of H2O significantly
affected the reaction rate for the deoxygenation of 1a with a kH/kD value of 3.9. These results rule out
the participation of H2 in the Au/HT-catalyzed deoxygenation reaction, while indicating that not only
CO functions as a sole reductant, but also water takes part in the deoxygenation. An additional
experiment using trans-2-octenal in place of 1a revealed that chemoselective reduction occurred to
give trans-2-octen-1-ol as the sole product while retaining the C=C double bond of the starting
material. From the above results, we believe that an active Au-hydride species is generated in situ from
the reaction of H2O with CO during the deoxygenation of epoxides. According to the proposed
reaction mechanism (Scheme 6), a basic site of HT facilitates the formation of the Au-hydride species
through the nucleophilic attack of OH− on the Au-CO species followed by a decarboxylation, which is
well evidenced by the positive effect of the additional base of Na2CO3 to the Au NPs on the non-basic
material of TiO2 (Table 3, Entry 6 vs. 7). Finally, to confirm the generation of the Au-H species,
Fourier transform infrared (FT-IR) studies of Au/HT were conducted in the presence of CO and H2O.
When Au/HT was treated with CO and H2O vapor at 298 K, a new band attributed to the generation of
Au-H species was detected around 1750 cm−1 (Figure 4). Next, this treated Au/HT was exposed to the
vapor of 1a, and the band attributed to the Au-H species gradually disappeared. The detection of the
Au-H species agreed with recent IR and theoretical studies on Au–H species that predicted a band
around 1800 cm−1 [44,45]. These above control experiments are consistent with the proposed reaction

Molecules 2011, 16
8219
mechanism as shown in Scheme 6. The heterolytic H+ and Au-hydride species generated in situ on
Au/HT deoxygenate the epoxide to form the corresponding alkene and water.
After the publication of our Au/HT-CO/H2O catalyst system, Cao et al. reported a deoxygenation
method using Au/TiO2-VS (very small gold NPs on TiO2) under water-gas shift reaction conditions [46].
Au/TiO2-VS showed high catalytic activity (TON = 9,600, TOF = 400 h−1) in the deoxygenation of
styrene oxide in the mixed solvent of acetone with H2O under a high pressure CO atmosphere (10 atm).
2.2.3. Selective Deoxygenation of Epoxides Using Molecular Hydrogen
The ideal green methodology for the catalytic deoxygenation of epoxides is to utilize molecular
hydrogen (H2) as a reductant due to the formation of non-toxic water as a by-product. However, the
use of H2 often causes non-selective reduction of epoxides to yield alcohols and alkanes as byproducts
through hydrogenation of the epoxides and overhydrogenation of the desired alkenes, respectively.
Although there are a few successful reports on the selective deoxygenation of epoxides using H2, high
selectivity for alkenes is restricted to low conversion levels [46] or a limited range of substrates [47].
Therefore, the development of an efficient catalytic system for the selective deoxygenation of epoxides
to the corresponding alkenes using H2 is a challenging task.
With supported Au NPs in hand, the deoxygenation conditions were optimized [38]. When the
deoxygenation of 1a using Au/HT was carried out at 80 °C under 1 atm of H2 for 6 h, 1a was
converted to 2a in 97% yield accompanied by the formation of ethylbenzene (3a) as a byproduct
through the hydrogenation of the desired product 2a (Table 5, Entry 1). Next, Au NPs on other
supports were investigated in the deoxygenation of 1a under similar reaction conditions. Au/CeO2 and
Au/Al2O3 had lower selectivities for 2a, which caused hydrogenation of 2a (Entries 4 and 5) [48].
Interestingly, Au/TiO2 gave 2a with over 99% selectivity, though the conversion of 1a was much
lower than that of Au/HT (Entry 6). Au/SiO2 did not exhibit any catalytic activity toward this reaction
(Entry 7). Remarkably, when the reaction was carried out at 60 °C for 8 h, Au/HT produced 2a in over
99% yield without formation of any side products (Entry 2). Moreover, the C=C bond of 2a was
completely intact when the reaction time was prolonged (Entry 3). The Au NP catalysis exhibited
different activity from other metal NPs. Ag/HT, Rh/HT, Ru/HT, and Cu/HT did not function as
catalysts for this reaction (Entries 10-13). On the other hand, Pd/HT and Pt/HT afforded undesired 4a
with over 99% selectivity through the hydrogenation of 1a (Entries 8 and 9).
a
Table 5. Deoxygenation of styrene oxide using H2 .
O
OH
Au catalyst (Au: 0.9 mol%)
+
+
H2 (1atm)
1a
0.5 mmol
2a
3a
4a
Temp. Time Conv. b Sel. for 2a b Sel. for 3a b Sel. for 4a b
Entry Catalyst
(°C)
80
(h)
6
(%)
97
(%)
97
(%)
3
(%)
0
1
2
3
Au/HT
Au/HT
Au/HT
60
60
8
24
>99
>99
>99
>99
0
0
0
0

Molecules 2011, 16
8220
Table 5. Cont.
Temp. Time Conv. b Sel. for 2a b Sel. for 3a b Sel. for 4a b
Entry Catalyst
(°C)
80
80
80
80
80
80
80
80
80
80
(h)
6
6
6
6
6
6
6
6
(%)
64
82
(%)
81
36
>99
-
0
0
-
-
-
(%)
19
64
<1
-
0
<1
-
(%)
0
0
0
4
5
6
7
8
Au/CeO2
Au/Al2O3
Au/TiO2
Au/SiO2
Pd/HT
26
<1
>99
87
<1
<1
<1
<1
-
>99
>99
-
-
-
-
9
Pt/HT
10
11
12
13
Ag/HT
Rh/HT
Ru/HT
-
-
-
6
6
Cu/HT
-
a
b
Reaction conditions: Catalyst (Au: 0.9 mol%), toluene (5 mL), 80 °C, 6 h; Determined by GC
using an internal standard technique.
Next, we conducted further studies on Au/HT and Au/TiO2 in the hydrogenation of 2a in the
presence or absence of p-methylstyrene oxide (1c) (Scheme 8). In the absence of 1c, Au/TiO2
hydrogenated 2a into 3a. Surprisingly, Au/HT did not show any activity toward the hydrogenation of
2a. Neither Au/HT nor Au/TiO2 hydrogenated 2a in the presence of 1c. These sharply contrasting
results indicate that the hydrogen species generated on Au/HT are active for the deoxygenation of
epoxides, but are completely inactive for the hydrogenation of C=C bonds. On the other hand, the high
selectivity of Au/TiO2 for alkenes in the deoxygenation of epoxides (Table 5, Entry 6) is attributable to
the preferential adsorption of epoxides over alkenes, which is a similar phenomenon to the previous
report that the nitro group in 3-nitrostyrene was reduced by Au/TiO2 catalyst while retaining C=C
bonds [49].
Scheme 8. Hydrogenation of 2a in the presence or absence of p-methylstyrene oxide.
Au cat. (Au: 0.9 mol%)
toluene (5 mL), H2 (1 atm), 60 oC, 8 h
2a
3a
0.5 mmol
Au/HT <1%
Au/TiO2 63%
O
Au cat. (Au: 0.9 mol%)
+
+
toluene (5 mL), H2 (1 atm), 60 oC, 8 h
2a
1c
3a
2c
0.5 mmol
0.5 mmol
Au/HT
Au/TiO2 <1%
0%
75%
14%
Various Au/HTs with different mean diameters of Au NPs were tested for the deoxygenation of 1a
with H2 (Figure 5). Different sized Au/HTs could be prepared by varying the concentration of HAuCl4
solution [38]. Interestingly, larger Au NPs (>3 nm) showed lower catalytic activity and selectivity for
the deoxygenation due to the hydrogenation of the C=C bond. The selectivity and yield of 2a increased
with decreasing mean diameter of supported Au NPs. From these results, it can be said that

Molecules 2011, 16
8221
immobilizing small Au NPs (<3 nm) is the key to promoting the selective deoxygenation of epoxides
to alkenes. The lower selectivity of larger Au NPs indicates that non-polar hydrogen species active for
the hydrogenation of C=C bond were easily generated on the surface of larger Au NPs through the
homolytic dissociation of H2. Au/HT with a mean diameter of 2.7 nm showed high catalytic activity
and selectivity for the H2-driven deoxygenation of both aromatic and aliphatic epoxides to alkenes
(Table 6). After the reaction, Au/HT could be reused with no loss of its catalytic efficiency (Entries 2
and 3).
Figure 5. Size effect on the deoxygenation of 1a.
O
Au/HT (Au: 0.9 mol%)
+
toluene (5 mL), H2 (1 atm), 80 oC, 6 h
1a
3a
2a
0.5 mmol
Table 6. Deoxygenation of various epoxides using Au/HT a.
O
Au/HT (0.9 mol%)
R2
R1
H2 (1 atm)
R1
R2
Time
(h)
Conv. b
(%)
Sel. b
(%)
Entry
Substrate
Product
1
O
8
8
8
>99
97
>99
>99
>99
2 c
3 d
97
O
4
5
6
12
12
24
81
84
85
>99
>99
>99
O
F
F
O
Cl
Cl

Molecules 2011, 16
8222
Table 6. Cont.
Time
(h)
Conv. b
(%)
Sel. b
(%)
Entry
Substrate
Product
O
7 e
12
98
96
>99
O
8 e
12
>99 (E/Z = 2/3)
O
9
24
24
84
89
>99
>99
O
10
OH
OH
11
24
92
>99
O
a
b
Reaction conditions: Au/HT (0.1 g), toluene (5 mL), substrate (0.5 mmol), 60 °C; Determined
by GC or HPLC using an internal standard technique; c Reuse 1; d Reuse 2; e At 100 °C.
Bearing in mind that basic ligands of transition-metal complexes promote heterolytic cleavage of H2
to give metal-hydride species, we propose a concerted effect between the basic sites of HT and Au NPs.
Namely, heterolytic cleavage of H2 occurs to give [Au-H]− and [HT-H]+ species at the interface
between Au NPs and HT, which then react with an epoxide to afford an alkene and H2O (Scheme 9).
The formation of [Au-H]− and [HT-H]+ was confirmed by FT-IR studies. When Au/HT was treated
with 50 mbar of H2, IR bands attributed to [Au-H]− and [HT-H]+ appeared around 1,748 cm−1 and
3,200 cm−1, respectively. The exclusive formation of the heterolytically cleaved hydrogen species of
Au-hydride and H+ on HT would selectively deoxygenate epoxides to alkenes.
Scheme 9. Heterolytic dissociation of H2 at the interface between Au NPs and basic sites
(BS) of HT in the deoxygenation of epoxides.
H-
H
H+
BS
+ H2O
H
R
R
H
H
Au
Au
Au
Au
BS
BS
BS
O
HT
HT
HT
HT
3. Experimental
3.1. General
All organic reagents were purified before use. The products were identified by GC, HPLC and
NMR analysis. Retention times (GC or HPLC) and chemical shifts (1H and 13C-NMR) of the products
were in agreement with those of authentic samples (commercially available). HAuCl4·H2O was
obtained from N. E. CHEMCAT. Co., Ltd. (Tokyo, Japan). MgO (GR for analysis) was purchased
from Merck Chemicals Japan Co., Ltd. (Tokyo, Japan). Al2O3 (JRC-ALO-3), SiO2 (JRC-SIO-6) and

Molecules 2011, 16
8223
TiO2 (JRC-TIO-4) were supplied by the Catalysis Society of Japan (Tokyo, Japan). Inductively
1
13
coupled plasma measurements were performed by SII Nano Technology SPS7800. H and C-NMR
spectra were recorded on JEOL JNM-AL400 and JNM-GSX270 spectrometers, respectively. GC
(Shimadzu GC-2014) analysis was carried out with a KOCL-3000T and column. High-performance
liquid chromatography (HPLC) was performed on a Shimadzu LC-10ADvp: STR ODS-IV. Atomic
force microscopy (AFM) and transmission electron microscopy (TEM) micrographs were obtained
with a Shimadzu SPM-9700 and Hitachi HF-2000 type microscope, respectively. Au L-edge X-ray
absorption spectra were collected in the quick mode and recorded at room temperature in transmission
mode at the facilities installed on the BL-01B1 line attached with a Si (311) monochromator at SPring-
8, Japan Atomic Energy Research Institute (JASRI), Harima, Japan. Data analysis was performed
using the REX 2000 program, ver. 2.5.7 (Rigaku). Fourier transformation (FT) of k3-weighted
extended X-ray absorption fine structure (EXAFS) data was performed to obtain the radial structural
function. FT-IR data were collected in a JASCO FT-IR 410 spectrometer equipped with a MCT
detector. Self-supporting pellets were prepared from the sample powders and treated directly in the IR
cell allowing thermal treatments under a controlled atmosphere.
3.2. Preparation of Au/HT
HT was prepared by the previously reported method [40]. Au/HT was synthesized as follows: HT
(1.0 g) was added to 50 mL of an aqueous HAuCl4 solution (2 mM). After stirring for 2 min, 0.09 mL
of aqueous NH3 solution (10%) was added. The mixture was further stirred at room temperature for
12 h. The obtained slurry was filtered and washed with deionized water, and dried in vacuo to afford
HT-supported Au(III) species [Au(III)/HT] as a pale yellow powder. Au(III)/HT (0.9 g) was subsequently
stirred in 50 mL of KBH4 solution (18 mM) under Ar atmosphere at room temperature for 1 h. The
solid was filtered and washed with deionized water to give Au/HT as a reddish purple powder.
4. Conclusions
We discovered that Au/HT catalyzed the highly efficient deoxygenation of epoxides to the
corresponding alkenes using various reductants. The obtained TON in the Au/HT-alcohol system was
three orders of magnitude greater than that of previous reports. An alternative catalytic deoxygenation
system was developed using CO/H2O as a reductant. The Au/HT-CO/H2O system could promote the
deoxygenation of epoxides under mild reaction conditions (water, at room temperature, under 1 atm of
CO). Under the water-gas shift reaction conditions, IR experiments revealed the in situ generation of
the Au-hydride species. Finally, Au/HT realized an ideal green deoxygenation of epoxides using H2 as
a reductant with water as the sole by-product. During these deoxygenations, no leaching of Au NPs
from Au/HT to the reaction mixture occurred and Au/HT could be reused with retention of its high
catalytic activity and selectivity. It is notable that the non-polar C=C bonds of products remained intact
during these deoxygenations. The key to the above successful deoxygenation is the in situ generated
Au-hydride and H+ species obtained through the concerted effect of the interface between Au NPs and
basic sites of HT. We believe that this Au NP catalysis can be applied to other chemoselective reductions.

Molecules 2011, 16
8224
Acknowledgments
This work was supported by a Grant-in-Aid for Young Scientists (A) (23686116) from the Japan
Society for the Promotion of Science (JSPS). We thank Uruga, Tanida, Nitta, Taniguchi and Hirayama
(SPring-8) for XAFS measurements. The TEM experiments were carried out at a facility of the
Research Center for Ultrahigh Voltage Electron Microscopy, Osaka University. One of the authors
A.N. thanks the JSPS Research Fellowships for Young Scientists. He also expresses his special thanks
to The Global COE (Center of Excellence) Program “Global Education and Research Center for Bio-
Environmental Chemistry” of Osaka University.
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