A new type of carbonylation of styrenes catalyzed by Pd(OAc)2 combined with molybdovanadophosphate

Article abstract of DOI:10.1246/bcsj.80.1194

A new type of carbonylation of styrenes was achieved under a 1:1 mixture of CO (0.5 atm) and O₂ (0.5 atm) in the presence of Pd(OAc)₂ combined with H₅PMo₁₀V₂O₄₀ nH ₂O to give 4-methyl-2-phenylnaphthalen-1(4H)-one in 78% yield. Various substituted styrenes were also carbonylated to the corresponding substituted arylnaphthalen-l(4H)-ones in moderate yields. The reaction was found to proceed in two stages involving the head-to-tail dimerization of styrenes, followed by carbonylation of the resulting dimers. Styrenes were efficiently dimerized under air (1 atm) in the absence of CO even at room temperature to produce head-to-tail dimers in good yields.

Full text of DOI:10.1246/bcsj.80.1194

1194 Bull. Chem. Soc. Jpn. Vol. 80, No. 6, 1194–1198 (2007)
Ó 2007 The Chemical Society of Japan
A New Type of Carbonylation of Styrenes Catalyzed
by Pd(OAc)2 Combined with Molybdovanadophosphate
ꢀ
Shingo Yamada, Yasushi Obora, Satoshi Sakaguchi, and Yasutaka Ishii
Department of Applied Chemistry & High Technology Research Center, Faculty of Engineering,
Kansai University, Suita, Osaka 564-8680
Received December 18, 2006; E-mail: ishii@ipcku.kansai-u.ac.jp
A new type of carbonylation of styrenes was achieved under a 1:1 mixture of CO (0.5 atm) and O2 (0.5 atm) in the
presence of Pd(OAc)2 combined with H5PMo10V2O40 nH2O to give 4-methyl-2-phenylnaphthalen-1(4H)-one in 78%
ꢁ
yield. Various substituted styrenes were also carbonylated to the corresponding substituted arylnaphthalen-1(4H)-ones
in moderate yields. The reaction was found to proceed in two stages involving the head-to-tail dimerization of styrenes,
followed by carbonylation of the resulting dimers. Styrenes were efficiently dimerized under air (1 atm) in the absence of
CO even at room temperature to produce head-to-tail dimers in good yields.
Palladium-catalyzed carbonylation of styrenes has been ex-
tensively investigated and reported to afford methyl cinna-
mate,1 2-phenylpropionate,2 and dimethyl 2-phenylsuccinate.3
The same strategy has been extended to asymmetrical carbox-
ylation and carbomethoxylation reactions.1,4 On the other
hand, the dimerization of styrene leading to head-to-tail dimers
is reported to be promoted by Pd complexes as well as several
transition-metal complexes.5 We found that styrenes under a
1:1 mixture of CO and O2 in the presence of Pd(OAc)2 com-
(0.5 atm) in the presence of Pd(OAc)2 (0.1 mmol) and HPMoV
(0.04 mmol) in acetic acid (5 mL) at 90 ꢂC for 15 h (standard
conditions) afforded trans-1,3-diphenyl-1-butene (2a) (7.5%)
and 4-methyl-2-phenylnaphthalen-1(4H)-one (3a) (75%),
which corresponds to a carbonylated product of dimer 2a
(Entry 1). It is interesting to note that the present reaction
did not promote the carbonylation of the double bond of 1a
leading to cinnamic acid and 2-phenylpropionic acid which
are usually obtained from carbonylation of 1a.1–3 Although
there have been numerous works on the carbonylation of 1a,
to our knowledge, the carbonylation of 1a to 3a has not yet
been reported.
It was found that the yield of 3a decreased with a decrease
in the amount of HPMoV, whereas the amount of dimer 2a in-
creased (Entries 2 and 3). These results indicate that the quan-
tity of the HPMoV catalyst is an important factor in promoting
the carbonylation of the resulting dimer. When the quantity of
the Pd(OAc)2 catalyst was reduced to half and one-tenth, the
yield of 3a gradually decreased (Entries 4 and 5). Needless
to say, no reaction took place in the absence of either HPMoV
or Pd(OAc)2 (Entries 6 and 7). To show the influence of the
concentration of CO and O2 on the present carbonylation,
the reaction was carried out under varying CO and O2 pres-
sures. Under higher concentrations of either CO or O2, the car-
bonylation of 1a to 3a was retarded, and the best result was ob-
tained under a 1:1 mixture of CO and O2 (Entries 8–11). The
reaction of 1a at 110 ꢂC gave almost the same results as that of
90 ꢂC, while the reaction at 70 ꢂC resulted in a slight decrease
in the yield of 3a (Entries 12 and 13).
bined with H5PMo10V2O40 26H2O (HPMoV) underwent se-
ꢁ
lective dimerization–carbonylation to give the corresponding
arylnaphthalen-1(4H)-ones in fair to good yields. To our
knowledge, this type of carbonylation of styrenes by a palladi-
um catalyst has scarcely been studied, so far. In this paper, we
report a new type of dimerization–carbonylation reaction of
styrenes under a mixture of CO and O2 catalyzed by Pd(OAc)2
and HPMoV (Eq. 1).
cat.Pd(OAc)2/HPMoV
R
AcOH
CO(0.5 atm)/O2(0.5 atm)
1a-g
1a: R = H, 1b: R = o-Me, 1c: R = m-Me
1d: R = p-Me, 1e: R = p-Cl, 1f: R = p-Br
1g: R = p-COOH
ð1Þ
+
R
R
R
R
O
2a-g
3a-g
The carbonylation of several substituted styrenes was exam-
ined under several reaction conditions (Table 2). o-, m-, and
p-Methyl styrenes, 1b, 1c, and 1d, led to the corresponding
methyl-substituted phenylnaphthalen-1(4H)-ones 3b, 3c, and
3d in fair yields along with small amounts of dimers 2b
(3.6%), 2c (3.4%), and 2d (4.5%), respectively (Entries 2–4).
Carbonylated products 3b and 3d were obtained as a single
isomer from 1b and 1d, respectively, but a 92:8 regioisomeric
mixture of 3c and 3c0 was obtained from 1c. However, car-
In order to confirm the optimum reaction conditions of the
present carbonylation, styrene (1a) was chosen as a model sub-
strate and allowed to react under various reaction conditions.
Table 1 shows the representative results for the carbonyla-
tion of 1a under a mixture of CO and O2 in the presence of
catalytic amounts of Pd(OAc)2 and H5PMo10V2O40 26H2O
(HPMoV).
The reaction of 1a under a 1:1 mixture of CO (0.5 atm)/O2
ꢁ
Published on the web June 13, 2007; doi:10.1246/bcsj.80.1194

S. Yamada et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 6 (2007) 1195
Table 1. Carbonylation of Styrene (1a) under CO and O2 by Pd(OAc)2 Combined with HPMoVaÞ
Pd(OAc)2/HPMoV
(mmol)
CO/O2
(atm)
Temp
/ꢂC
Conv.
/%
Yield/%bÞ
3a
75
Entry
2a
1
2
3
4
5
6
7
8
9
10
11
12
13
0.1/0.04
0.1/0.02
0.1/0.01
0.05/0.04
0.01/0.04
0/0.04
0.5/0.5
0.5/0.5
0.5/0.5
0.5/0.5
0.5/0.5
0.5/0.5
0.5/0.5
0.3/0.7
0.1/0.9
0.7/0.3
0.9/0.1
0.5/0.5
0.5/0.5
90
90
90
90
90
90
90
90
90
90
90
110
70
>99
>99
>99
>99
>99
7.5
21
42
19
30
10
42
37
1.6
no reaction
no reaction
0.1/0
0.1/0.04
0.1/0.04
0.1/0.04
0.1/0.04
0.1/0.04
0.1/0.04
>99
>99
>99
>99
>99
>99
6.6
11
3.9
32
6.6
7.6
45
32
54
9.5
78(66)
49
a) Styrene (1a) (2 mmol) was allowed to react in the presence of Pd(OAc)2 and H5PMo10V2O40
26H2O (HPMoV) under CO and O2 in AcOH (5 mL) at 70–110 ꢂC for 15 h. b) GC yields. The number
in parentheses shows isolated yield.
ꢁ
bonylated products were not obtained from p-chlorostyrene
(1e), p-bromostyrene (1f), and p-vinylbenzoic acid (1g), be-
cause they easily polymerized under these conditions (Entries
5–7).
Since the present reaction was considered to proceed
through the formation of dimer 2a, the reaction of 1a under
the standard conditions (Entry 1 in Table 1) was followed by
GC at suitable time intervals (Fig. 1).
The time-conversion curves for the reaction indicate that 2a
is quickly formed and then slowly carbonylated to 3a. These
results prompted us to carry out the carbonylation of styrene
dimer 2a under several conditions (Table 3).
The reaction of 2a under standard conditions afforded 3a in
53% yield at 99% conversion of 2a (Entry 1). Under the pres-
ent reaction conditions, a prolonged reaction resulted in the de-
composition of 3a. When the reaction time was shortened to
8 h, the yield of 3a increased to 78% (Entry 2). Carbonylation
at 65 ꢂC for 15 h produced 3a in 70% yield (Entry 3), but no
carbonylation took place at room temperature (Entry 4). From
the carbonylation under several varying CO and O2 pressure, a
1:1 mixture of CO and O2 was found to be best for the carbon-
ylation of 2a (Entries 5 and 6). The reaction with CO alone
afforded 3a in poor yield (Entry 7), probably because of the
difficulty to regenerate of PdII from Pd0 in the absence of
O2. Removing either HPMoV or Pd(OAc)2 from the catalytic
system resulted in no or a trace amount of 3a (Entries 8 and 9).
On the basis of these results, each step of carbonylation of
styrenes, i.e., dimerization and carbonylation was examined
in one-pot. The dimerization was carried out in the presence
of Pd(OAc)2 (0.1 mmol) and HPMoV (0.04 mmol) in acetic
acid (5 mL) under air (1 atm) at 25–50 ꢂC for 2–6 h, and then,
the mixture was reacted under CO (0.5 atm) and O2 (0.5 atm)
at 70–90 ꢂC for 15 h (Table 4).
respectively (Entries 5–7). After completion of the dimeriza-
tion, the air in the reaction system was replaced with a mixture
of CO (0.5 atm) and O2 (0.5 atm) and allowed to react under
prescribed conditions. In the same manner as 2a, all of the di-
mers, except for p-bromostyrene dimer 2f and p-vinylbenzoic
acid dimer 2g, were carbonylated to give the corresponding
products 3b–3e in 45–78% yields (Entries 1–5). However,
no carbonylation products were obtained from 2f and 2g, be-
cause of the formation of a complex mixture of polymerized
products (Entries 6 and 7).
It is thought that the reaction proceeds through alkene coor-
dination of the dimer 2 to PdII, followed by orthopalladation to
the aryl group of 2. Subsequent CO insertion and reductive
elimination affords 3 and a Pd0 spiecies, which is reoxidized
with O2 to PdII by the action of HPMoV.
In conclusion, we found that the reaction of styrene deriva-
tives under CO and O2 in the presence of Pd(OAc)2 and
HPMoV afforded styrene dimers and their carbonylated prod-
ucts, phenylnaphthalen-1(4H)-ones, as the major products. The
present reaction is thought to be a new type of the carbonyla-
tion of styrenes. In addition, it was found that styrenes effi-
ciently dimerized in the Pd(OAc)2/HPMoV catalytic system
under air at room temperature to afford head-to-tail styrene
dimers in high yields.
Experimental
All solvents and reagents were purchased from commercial
sources and used without further treatment. GC analysis was per-
formed on a GC, equipped with a flame ionization detector using
a 0:22 mm ꢃ 25 m capillary column (BP-5). Mass spectra were
determined at ionization energy of 70 eV on a GCMS. 1H and
13C NMR were measured at 400 and 100 MHz, respectively, in
CDCl3 with Me4Si as an internal standard.
Styrene 1a and o-, m-, and p-methyl styrenes 1b, 1c, and
1d smoothly dimerized by Pd(OAc)2 combined with HPMoV
under air even at room temperature to afford the correspond-
ing styrene dimers, 2a, 2b, 2c, and 2d, in 96, 77, 74, and
67% yields, respectively (Entries 1–4). Substrates, 1e–1g also
dimerized to give dimers 2e–2g in 88, 80, and 57% yields,
Typical Procedure for the Carbonylation of Styrene (1a).
A solution of Pd(OAc)2 (22 mg, 0.1 mmol), HPMoV (88 mg, 0.04
mmol), and styrene (1a) (208 mg, 2 mmol) in acetic acid (5 mL)
was placed in a flask (30 mL). The flask was filled with a mixture
of CO (0.5 atm) and O2 (0.5 atm), and the reaction mixture was al-
lowed to react while stirring at 90 ꢂC for 15 h. The reaction was

1196 Bull. Chem. Soc. Jpn. Vol. 80, No. 6 (2007)
Dimerization–Carbonylation of Styrenes
Table 2. One-Step Carbonylation of Substituted Styrenes by
Pd(OAc)2 Combined with HPMoVaÞ
80
60
40
20
0
3a
Entry Substrate
Temp/ꢂC Time/h Product Yield/%bÞ
Ph
O
1
110
60
15
15
3a
3b
78 (66)
48 (40)
1a
2cÞ
1b
2a
Ph
3d),e)
70
70
80
80
80
13
15
15
15
15
3c
3d
3e
3f
68 (66)
57 (52)
1
1c
0
3
6
9
12
15
Time / h
4fÞ
Fig. 1. Time-conversion curves for carbonylation of sty-
rene (1a) by Pd(OAc)2/HPMoV under the same condi-
tions as Entry 1 in Table 1.
1d
5
Cl
1e
Table 3. Carbonylation of Styrene Dimer 2a by Pd(OAc)2
Combined with HPMoVaÞ
6
n.d.gÞ
n.d.gÞ
Entry CO/O2 Temp/ꢂC Time/h Conv./% 3a/%bÞ
(atm)
Br
1f
1
2
3
4
5
6
7
0.5/0.5
0.5/0.5
0.5/0.5
0.5/0.5
0.3/0.7
0.7/0.3
1.0/0
90
90
65
25
65
65
65
65
65
15
8
99
92
88
53
78
70
7
3g
HOOC
1g
15
15
15
15
15
15
15
no reaction
a) Styrenes 1a–1g (2 mmol) were allowed to react in the pres-
ence of Pd(OAc)2 (0.1 mmol) and HPMoV (0.04 mmol) under
CO (0.5 atm)/O2 (0.5 atm) in AcOH (5 mL). b) GC yields. The
numbers in parentheses show isolated yields. c) Pd(OAc)2
(0.2 mmol) was used. d) Pd(OAc)2 (0.15 mmol) was used.
e) A 92:8 mixture of 3c and 3c0 was obtained. f) EtCO2H
(5 mL) was used. g) Not detected by GC.
87
91
28
4
64
77
1.8
<1
n.d.eÞ
8cÞ
9dÞ
0.5/0.5
0.5/0.5
49
a) 2a (1 mmol) was allowed to react in the presence of
Pd(OAc)2 (0.1 mmol) and HPMoV (0.04 mmol) under CO and
O2 in AcOH (5 mL). b) GC yields. c) The reaction was carried
out in the presence of Pd(OAc)2 (0.5 mmol) without HPMoV.
d) The reaction was carried out in the presence of HPMoV
(0.04 mmol) without Pd(OAc)2. e) Not detected by GC.
O
O
3c
3c'
calcd for C17H14O [M]þ 234.1045, found 234.1048.
quenched with acetone, and the solution was filtered. GC measure-
ment of the liquid indicated that trans-1,3-diphenyl-1-butene (2a)
(7.5%) and 4-methyl-2-phenylnaphthalen-1(4H)-one (3a) (75%)
are formed as the major products. The conversions and yields of
products were estimated from the peak areas based on the internal
standard technique. The products were isolated by column chro-
matography (230–400 mesh silica gel, hexane:ethyl acetate =
4,5-Dimethyl-2-o-tolyl-1(4H)-naphthalenone (3b): 1H NMR
(400 MHz, CDCl3) ꢀ 1.21 (d, J ¼ 7:1 Hz, 3H), 2.43 (s, 3H), 2.45
(s, 3H), 4.36–4.41 (m, 1H), 7.25–7.59 (m, 6H), 7.76 (d,
J ¼ 7:6 Hz, 1H), 7.85 (d, J ¼ 1:7 Hz, 1H); 13C NMR (100 MHz,
CDCl3) ꢀ 17.7 (CH3), 18.2 (CH3), 20.1 (CH3), 35.7 (CH), 121.9
(CH), 126.0 (CH), 127.8 (CH), 128.4 (CH), 129.0 (CH), 130.5
(CH), 131.7 (CH), 134.3 (CH), 135.0 (C), 136.2 (C), 137.1 (C),
138.4 (C), 142.3 (C), 154.0 (C), 194.2 (C); IR (neat, cmꢄ1) 720,
752, 767, 1045, 1275, 1620, 1687, 2966, 3000 cmꢄ1; GC-MS
(EI, 70 eV) m=z 77, 91, 116, 141, 229, 247, 262 [M]þ; HRMS
(EI, 70 eV) m=z calcd for C19H18O [M]þ 262.1358, found
262.1346.
4,6-Dimethyl-2-m-tolyl-1(4H)-naphthalenone (3c): 1H NMR
(400 MHz, CDCl3) ꢀ 1.21 (d, J ¼ 6:7 Hz, 3H), 2.23 (s, 3H), 2.28
(s, 3H), 4.11–4.16 (m, 1H), 6.99–7.28 (m, 6H), 7.45 (s, 1H), 7.62
(d, J ¼ 7:8 Hz, 1H); 13C NMR (100 MHz, CDCl3) ꢀ 18.6 (CH3),
19.1 (CH3), 21.4 (CH3), 36.3 (CH), 122.2 (CH), 127.7 (CH), 128.6
(CH), 129.4 (CH), 130.0 (CH), 131.6 (CH), 133.2 (CH), 134.0
(C), 134.2 (CH), 134.9 (C), 138.3 (C), 139.2 (C), 141.0 (C),
1
10:1) and were characterized by H, 13C NMR, GC-MS, and IR.
Compounds 2a,5b 2b,6 2c,7 2d,8 2e,5d 2f,5b and 2g5b have been
reported previously.
4-Methyl-2-phenyl-1(4H)-naphthalenone (3a):
1H NMR
(400 MHz, CDCl3) ꢀ 1.37 (d, J ¼ 6:8 Hz, 3H), 4.35–4.40 (m, 1H),
7.34–7.44 (m, 4H), 7.52 (d, J ¼ 7:3 Hz, 1H), 7.58–7.65 (m, 4H),
7.87 (d, J ¼ 7:3 Hz, 1H); 13C NMR (100 MHz, CDCl3) ꢀ 18.8
(CH3), 36.7 (CH), 124.2 (CH), 125.0 (CH), 127.7 (CH), 128.7
(CH), 129.3 (CH), 130.8 (CH), 133.8 (CH), 134.7 (CH), 134.8
(C), 136.7 (C), 140.7 (C), 155.9 (C), 194.1 (C); IR (neat, cmꢄ1
)
570, 736, 765, 1631, 1697, 2968 cmꢄ1; GC-MS (EI, 70 eV) m=z
77, 91, 116, 128, 191, 219, 234 [M]þ; HRMS (EI, 70 eV) m=z

S. Yamada et al.
Bull. Chem. Soc. Jpn. Vol. 80, No. 6 (2007) 1197
Table 4. Dimerization and Carbonylation of Substituted Styrenes by Pd(OAc)2 Combined with HPMoVaÞ
Dimerization
Time/h
Carbonylation
Time/h
Entry
Substrate
Temp/ꢂC
rt
Yield/%bÞ
Temp/ꢂC
80
Yield/%bÞ
1
2
2
3
2a (96)
15
15
3a (78)
1a
1b
50
2b (77)
90
3b (54)
3cÞ
rt
rt
rt
rt
rt
6
5
2
2
4
2c (74)
2d (67)
2e (88)
2f (80)
2g (57)
70
90
90
90
90
15
15
15
15
15
3c (68)
1c
1d
4
3d (56)
5
3e (45)
Cl
1e
1f
6
3f (n.d.)dÞ
3g (n.d.)dÞ
Br
7eÞ
HOOC
1g
a) Styrenes 1a–1g (2 mmol) were allowed to react in the presence of Pd(OAc)2 (0.1 mmol) and HPMoV
(0.04 mmol) under air (1 atm) in AcOH (5 mL) at 20–50 ꢂC for 2–6 h, and then at 70–90 ꢂC for 15 h after
replacing air by CO (0.5 atm)/O2 (0.5 atm). b) GC yields. c) A 92:8 mixture of 3c and 3c0. d) Not detected
by GC. e) AcOH (2 mL) was used.
156.7 (C), 195.0 (C); IR (neat, cmꢄ1) 693, 787, 1113, 1324, 1609,
1628, 1696, 2925, 2965 cmꢄ1; GC-MS (EI) m=z 77, 91, 116, 141,
247, 262 [M]þ; HRMS (EI, 70 eV) m=z calcd for C19H18O [M]þ
262.1358, found 262.1356.
4.33–4.38 (m, 1H), 7.43 (d, J ¼ 8:5 Hz, 2H), 7.48–7.61 (m, 5H),
7.84 (s, 1H); 13C NMR (100 MHz, CDCl3) ꢀ 18.7 (CH3), 36.3
(CH), 124.1 (CH), 126.3 (CH), 129.1 (CH), 132.0 (CH), 132.9
(C), 133.2 (C), 134.2 (C), 134.9 (CH), 135.7 (CH), 138.2 (C),
140.8 (C), 153.7 (C), 192.6 (C); IR (neat, cmꢄ1) 593, 723, 825,
1093, 1254, 1491, 1589, 1622, 1693 cmꢄ1; GC-MS (EI) m=z 77,
91, 116, 141, 247, 262, 302 [M]þ; HRMS (EI) m=z calcd for
C17H12OCl2 [M]þ 302.0265, found 302.0273. Anal. Found: C,
67.23; H, 3.98%. Calcd for C17H12Cl2O: C, 67.35; H, 3.99%.
4,8-Dimethyl-2-m-tolyl-1(4H)-naphthalenone (3c0): 1H NMR
(400MHz, CDCl3) ꢀ 1.38 (d, J ¼ 6:8 Hz, 3H), 2.40 (s, 3H), 2.74 (s,
3H), 4.32–4.37 (m, 1H), 7.13–7.48 (m, 7H), 7.56 (d, J ¼ 1:7 Hz,
1H); 13C NMR (100 MHz, CDCl3) ꢀ 18.6 (CH3), 19.1 (CH3), 21.4
(CH3), 36.3 (CH), 122.2 (CH), 127.6 (CH), 128.3 (CH), 128.5
(CH), 129.4 (CH), 129.9 (CH), 131.6 (CH), 133.1 (CH), 134.0
(C), 134.9 (C), 138.3 (C), 139.2 (C), 141.0 (C), 156.6 (C), 195.0
(C); IR (neat, cmꢄ1) 702, 785, 1226, 1262, 1478, 1594, 1627,
1693, 2924, 2963 cmꢄ1; GC-MS (EI) m=z 77, 91, 116, 141, 247,
262 [M]þ. HRMS (EI) m=z calcd for C19H18O [M]þ 262.1358,
found 262.1359.
4,7-Dimethyl-2-p-tolyl-1(4H)-naphthalenone (3d): 1H NMR
(400 MHz, CDCl3) ꢀ 1.39 (d, J ¼ 6:9 Hz, 3H), 2.40 (s, 3H), 2.44
(s, 3H), 4.32–4.40 (m, 1H), 7.24–7.56 (m, 6H), 7.62 (d, J ¼ 1:6
Hz, 1H), 7.70 (s, 1H); 13C NMR (100 MHz, CDCl3) ꢀ 18.9
(CH3), 21.1 (CH3), 21.5 (CH3), 36.4 (CH), 124.1 (CH), 124.7
(CH), 129.5 (CH), 131.0 (CH), 132.0 (C), 133.7 (CH), 136.0
(CH), 137.0 (C), 137.6 (C), 139.7 (C), 140.0 (C), 153.4 (C),
194.3 (C); IR (neat, cmꢄ1) 753, 1160, 1281, 1608, 1626, 1693,
2968 cmꢄ1; GC-MS (EI) m=z 77, 91, 116, 141, 247, 262 [M]þ;
HRMS (EI) m=z calcd for C19H18O [M]þ 262.1358, found
262.1361.
This work was supported by a Grant-in-Aid for Scientific
Research on Priority Areas ‘‘Advanced Molecular Transforma-
tions of Carbon Resources’’ from the Ministry of Education,
Culture, Sports, Science and Technology, Japan, and the
‘‘High-Tech Research Center’’ Project for Private Universities:
matching fund subsidy from the Ministry of Education,
Culture, Sports, Science and Technology, Japan, 2005–2009.
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