Calcium phosphate-vanadate apatite (CPVAP)-catalyzed aerobic oxidation of propargylic alcohols with molecular oxygen

Article abstract of DOI:10.1016/j.tet.2004.08.004

Calcium phosphate-vanadate apatite (CPVAP) works effectively as a catalyst for the aerobic oxidation of propargylic alcohols to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Moreover, CPVAP can be readily separated by filtration and reused at least 10 times without appreciable loss of the catalytic activity.

Full text of DOI:10.1016/j.tet.2004.08.004

Tetrahedron 60 (2004) 9031–9036
Calcium phosphate-vanadate apatite (CPVAP)-catalyzed aerobic
oxidation of propargylic alcohols with molecular oxygen
b
Yasunari Maeda,a Yosuke Washitake,a Takahiro Nishimura,a, Keisuke Iwai,
*
Takayoshi Yamauchib and Sakae Uemuraa,
*
aDepartment of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku,
Kyoto 615-8510, Japan
bNissei Chemicals Inc., Yodogawa-ku, Osaka 532-0001, Japan
Received 21 June 2004; revised 4 August 2004; accepted 4 August 2004
Available online 1 September 2004
Abstract—Calcium phosphate-vanadate apatite (CPVAP) works effectively as a catalyst for the aerobic oxidation of propargylic alcohols to
the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Moreover, CPVAP can be readily separated by
filtration and reused at least 10 times without appreciable loss of the catalytic activity.
q 2004 Elsevier Ltd. All rights reserved.
1. Introduction
reuse of the catalyst from the viewpoint of green and
sustainable chemistry, and eventually we disclosed that
calcium phosphate-vanadate apatite (we abbreviate this as
CPVAP), prepared by the reported method,7 could be used
as a recyclable catalyst for the aerobic oxidation of
propargylic alcohols. The CPVAP has been known to be
formed by partial substitution of PO34K by VO43K in
hydroxyapatite as a highly stable, isomorphic compound
Ca10(PO4)6Kx(VO4)x(OH)2.7 Herein, we report the CPVAP-
catalyzed oxidation of propargylic alcohols under an
atmospheric pressure of oxygen.
For the increasing environmental and economical concerns
in recent years, it is now essential for chemists to search
environmentally benign catalytic reactions as many as
possible. The organic reaction using heterogeneous catalyst
is one of the suitable methods for realizing green and
sustainable chemistry and much attention has been paid to it
because of its reusability and the ability to minimize the
toxic wastes.1,2 Recently, metal-immobilized hydroxyapa-
tite has been developed by Kaneda and co-workers, in which
the aerobic oxidation of organic compounds was well
studied.3 Especially, ruthenium and palladium-hydroxyapa-
tite (RuHAP or PdHAP) were revealed to be excellent
catalysts for the aerobic oxidation of alcohols, amines, and
silanes.3a–d
2. Results and discussion
First, the oxidation of 1-phenyl-2-propyn-1-ol (1a)
(0.5 mmol) was examined using the catalytic amount of
CPVAP (25 mg, 0.073 mmol (15 mol% to 1a) as vanadium)
in acetonitrile (1 mL) at 80 8C under an atmospheric
pressure of oxygen similar to the reaction conditions of
homogeneous catalytic system that we previously reported.5
The reaction, however, did not proceed efficiently to give
the corresponding ketone 2a even after a longer reaction
time (Table 1, entries 1–3). On the other hand, 2a was
obtained in high yield at higher temperature using
benzonitrile as solvent in the presence of the doubled
amount of CPVAP (50 mg, 0.15 mmol as vanadium) (entry
4). Other solvents such as toluene, chlorobenzene, and n-
butyronitrile were also examined (entries 5–7), because
benzonitrile was not easy to be removed after the reaction
due to its high boiling nature. When n-butyronitrile was
used as solvent, 2a was obtained in a similar high yield as in
We have so far studied the oxidation of alcohols using
molecular oxygen as a sole reoxidant, in which both
homogeneous and heterogeneous Pd-catalytic systems were
disclosed to be quite effective for the oxidation of various
kinds of alcohols.2d,e,4 We also found the effective oxidation
system for propargylic alcohols consisting of an oxovana-
˚
dium complex such as VO(acac)2, molecular sieves 3 A
(MS3A), and molecular oxygen in acetonitrile,5,6 the
oxidation of which was unsuccessful with Pd catalysts.
We have now tried to heterogenize this vanadium system for
Keywords: Vanadium; Oxidation; Propargylic alcohols; Molecular oxygen;
Hydroxyapatite.
* Corresponding authors. Tel./fax: C81-75-383-2517; e-mail
addresses: takahiro@scl.kyoto-u.ac.jp; uemura@scl.kyoto-u.ac.jp
0040–4020/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2004.08.004

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Y. Maeda et al. / Tetrahedron 60 (2004) 9031–9036
Table 1. Optimization of the reaction
Entry
Solvent
Temperature (8C)
Reaction time (h)
CPVAP (mg)
Conversion of 1a
(%)
Yield of 2a (%)a
1
2
3
4
5
6
7
8d
Acetonitrile
Acetonitrile
Acetonitrile
Benzonitrile
Toluene
Chlorobenzene
n-Butyronitrile
n-Butyronitrile
80
80
80
100
100
100
100
100
3
24
72
20
20
20
20
20
25b
25
25
50c
50
50
50
50
16
24
35
99
38
78
92
0
10
16
34
82
38
53
85
0
a
Based on 1a employed.
15 mol% as V to 1a.
30 mol% as V to 1a.
Under N2 (1 atm).
b
c
d
the use of benzonitrile (entry 7). The reaction under nitrogen
atmosphere did not proceed at all (entry 8), showing that the
presence of oxygen is essential for this reaction.
atmospheric pressure of air, 1a was also converted to 2a in
good yield although it proceeded slower than the same
reaction under molecular oxygen (entry 2). Among 1-aryl-2-
propyn-1-ols, those having a chloro or methyl substituent at
m- or p-position on aromatic nuclei (1e–1h) were efficiently
oxidized to give the corresponding ketones in high yields
(entries 6–9), while the oxidation of the alcohols having a
substituent at o-position (1b–1d) was slower (entries 3–5).
This tendency was also observed when propargylic alcohol
having a 1-naphthyl substituent (1i) was compared with that
having 2-naphthyl one (1j) (entries 10 and 11). Propargylic
alcohol having a vinylic substituent at the a-position (1k)
gave the corresponding ketone in low yield under this
condition (entry 12). Primary propargylic alcohol 1l was
converted to the corresponding aldehyde in good yield
(entry 13). The oxidation of propargylic alcohols having an
alkyl substituent at the a-position (1m–1o) gave the
corresponding ketones in low yields (entries 14, 17, and
18). Longer reaction time and higher reaction temperature
did not improve much the product yields (entries 15 and 16).
Next, we examined recycling of the catalyst. At first, the
oxidation of 1a in benzonitrile was carried out in the
presence of CPVAP (50 mg, 0.15 mmol as vanadium) at
100 8C for 20 h under oxygen atmosphere. After the
reaction, CPVAP was separated by filtration from the
reaction mixture, and the collected CPVAP was washed
with diethyl ether and dried under vacuum at room
temperature before use for the next run. The yield of 2a
was determined by GLC analysis. As a result, CPVAP could
be reused at least 10 times keeping in high catalytic activity
(Table 2). Similar phenomenone was also observed using n-
butyronitrile as solvent also shown in Table 2.
The oxidation of some propargylic alcohols was examined
in n-butyronitrile as solvent. Typical results are listed in
Table 3. When the reaction was carried out under an
The amount of the catalyst could be reduced in the oxidation
of some propargylic alcohols listed in Table 3 which
smoothly reacted to give the corresponding carbonyl
compounds in good yields (Table 4). Although the higher
reaction temperature was needed, the turnover number
(TON) reached to 4,400 when the reaction was carried out in
benzonitrile at 140 8C under S/CZ10,000 for 24 h (Eq (1)).
Table 2. Recycling of the catalyst
Run
Conversion of 1a (%)a
Yield of 2a (%)a,b
1
2
3
4
5
6
7
99 (92)
99 (84)
99 (84)
99 (84)
99 (83)
95 (79)
95
82 (85)
78 (82)
83 (80)
86 (81)
87 (82)
92 (74)
91
We next investigated a time profile of the oxidation of 1a
under the conditions shown in Table 4. The product yield
gradually increased and reached to maximum after ca. 20 h
(Fig. 1). When CPVAP was removed by filtration from the
reaction mixture after 9 h and the heating of the filtrate was
continued under the same conditions, the yield of 2a did not
improve at all. Further, no leaching of vanadium into the
filtrate was detected by ICP (inductivity coupled plasma)
atomic emission analysis. These results clearly show that
8
9
10
11
92
94
86
88
88
92
86
87
a
The results using n-butyronitrile as solvent are shown in parentheses.
Based on 1a employed.
b

Y. Maeda et al. / Tetrahedron 60 (2004) 9031–9036
9033
Table 3. CPVAP-catalyzed aerobic oxidation of propargylic alcohols
Entry
1
Substrate
Conversion of 1 (%)
Yield of 2 (%)a
1a RZH
89
85b
2c
3
4
5
6
7
8
9
1a RZH
73
59
80
55
89
99
99
98
64b
56
53
41
79
99
91
87
1b RZ2-Cl
1c RZ2-Me
1d RZ2-OMe
1e RZ3-Cl
1f RZ3-Me
1g RZ4-Cl
1h RZ4-Me
10
1i
72
52
11
12
1j
87
99
87
1k
31d
13
14
1l
74
31
66
1m
20b
15e
1m
1m
79
—
41b,d
31b,d
16f,g
17
1n
89
37
18
1o
50
24
a
Based on an alcohol employed.
GLC yield.
Under air (1 atm).
Many unidentified products were also observed.
For 48 h.
For 96 h.
b
c
d
e
f
g
Benzonitrile was used as solvent at 120 8C.
any vanadium species do not leach to the solution and the
oxidation may proceed on the surface of the solid catalyst.
hydroxyapatite (VHAP) prepared by Kaneda’s method8
as a catalyst gave 2a in moderate yield (entry 2). When
RuHAP and PdHAP, which were known to be effi-
cient catalysts for the aerobic oxidation of alcohols,3a,c
were used as catalysts, 2a was not obtained at all
(entries 3–6).
Lastly, we investigated the catalytic activity of other
transition metal-containing hydroxyapatites. The results
are summarized in Table 5. The use of vanadium

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Y. Maeda et al. / Tetrahedron 60 (2004) 9031–9036
Table 4. Reducing of the catalyst
4. Experimental
4.1. General
NMR spectra were recorded on JEOL EX-400 (1H NMR,
400 MHz; 13C NMR, 100 MHz) instruments for solutions in
CDCl3 with Me4Si as an internal standard: the following
abbreviations are used: s, singlet; d, doublet; t, triplet; m,
multiplet. GLC analyses were performed on a Shimadzu
GC-14A instrument (25 m!0.33 mm, 5.0 mm film thick-
ness, Shimadzu fused silica capillary column HiCap
CBP10-S25-050) with a flame-ionization detector and
helium as carrier gas. Analytical thin-layer chromatography
(TLC) was performed with Merck silica gel 60 F-254 plates.
Column chromatography was performed with Merck silica
gel 60. ICP atomic emission analysis for the vanadium
content in the CPVAP was performed with a Shimadzu
ICPS-1000 sequential plasma spectrometer.
Entry
Substrate
Yield of 2 (%)a
TON
1b
2
3
4
1a
1e
1f
1g
1h
97
78
72
89
82
48.5
39
36
44.5
42
5
a
Based on an alcohol employed.
For 24 h.
b
4.2. Materials
Commercially available organic and inorganic compounds
were used without further purification except for the
solvent. Alcohols 1a, 1m, 1o are commercial products and
purified by normal methods just before use. Alcohols 1b–1l
and 1n were prepared from the corresponding aldehydes and
lithium acetylides or alkynylmagnesium bromides, purified
by column chromatography on silica gel (eluent; n-hexane–
ethyl acetate) and identified by 1H NMR and 13C NMR. All
propargylic alcohols and the corresponding aldehydes and
ketones are known compounds. Ketone 2m is commercial
products. Selected spectral data of alcohols and carbonyl
compounds are shown below. Spectral data of other alcohols
and carbonyl compounds were shown in the previous
report.5b
Figure 1. Time profile of CPVAP-catalyzed aerobic oxidation of 1a.
4.2.1. 1-(o-Tolyl)-2-propyn-1-ol.9 (1c, Table 3, entry 4)
Yellow oil; H NMR (400 MHz, CDCl3) d 2.30 (br s, 1H
1
3. Conclusion
(OH)), 2.44 (s, 3H), 2.64 (d, JZ2.4 Hz, 1H), 5.61 (d, JZ
2.4 Hz, 1H), 7.17–7.27 (m, 3H), 7.65–7.69 (m, 1H); 13C
NMR (100 MHz, CDCl3) d 18.9, 62.2, 74.7, 83.2, 126.2,
126.3, 128.5, 130.7, 135.8, 137.7.
In summary, we found that calcium phosphate-vanadate
apatite (CPVAP) worked effectively as a catalyst for the
aerobic oxidation of propargylic alcohols to the correspond-
ing carbonyl compounds under an atmospheric pressure of
molecular oxygen. Moreover, CPVAP was readily separ-
ated by filtration and could be reused at least 10 times.
4.2.2. 1-(2-Methoxyphenyl)-2-propyn-1-ol.10 (1d, Table
3, entry 5) Yellow oil; 1H NMR (400 MHz, CDCl3) d 2.60
Table 5. Comparison with results using other transition metal containing hydroxyapatite as catalyst
Entry
Catalyst
Solvent
Conversion of 1a (%)
Yield of 2a (%)a
1
2
3
4
5
6
CPVAP
VHAPb
RuHAPb
RuHAPb
PdHAPb
PdHAPb
n-Butyronitrile
n-Butyronitrile
Toluene
n-Butyronitrile
Benzotrifluoride
n-Butyronitrile
97
49
62
10
100
100
97
39
2c
5
0c
0c
a
Based on alcohol employed.
Prepared by following the method described by Kaneda et al.3a,3c,8
Many unidentified products were also observed.
b
c

Y. Maeda et al. / Tetrahedron 60 (2004) 9031–9036
9035
(d, JZ2.4 Hz, 1H), 3.15 (br s, 1H (OH)), 3.88 (s, 3H), 5.69
(d, JZ2.4 Hz, 1H), 6.90 (d, JZ8.3 Hz, 1H), 6.97 (td, JZ
8.3, 1.5 Hz, 1H), 7.31 (td, JZ7.8, 1.5 Hz, 1H), 7.56 (dd, JZ
7.8, 1.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 55.5, 60.9,
74.0, 83.0, 110.7, 120.7, 127.7, 128.1, 129.7, 156.5.
20 mL Schlenk flask was added a propargylic alcohol
(0.5 mmol). Oxygen gas was then introduced into the flask
from an O2 balloon under atmospheric pressure and then the
mixture was stirred vigorously for 20 h at 100 8C under
oxygen. After the reaction, the mixture was cooled to room
temperature and CPVAP was separated by filtration through
a glass filter. The amount of the product was determined by
GLC analysis using bibenzyl as an internal standard. For
isolation of the product the solvent was evaporated and the
residue was purified by column chromatography on SiO2 (n-
4.2.3. 1-(3-Chlorophenyl)-2-propyn-1-ol.11 (1e, Table 3,
entry 6) Yellow oil; 1H NMR (400 MHz, CDCl3) d 2.37 (br
s, 1H (OH)), 2.70 (d, JZ2.2 Hz, 1H), 4.54 (d, JZ2.2 Hz,
1H), 7.31–7.44 (m, 3H), 7.56 (s, 1H); 13C NMR (100 MHz,
CDCl3) d 63.7, 75.3, 82.7, 124.6, 126.7, 128.6, 129.8, 134.4,
141.7.
1
hexane–ethyl acetate as an eluent) and identified by H
NMR and 13C NMR.
4.4.1. 1-(o-Tolyl)-2-propyn-1-one.13 (2c, Table 3, entry 4)
Yellow oil; 1H NMR (400 MHz, CDCl3) d 2.63 (s, 3H), 3.38
(s, 1H), 7.27 (d, JZ7.1 Hz, 1H), 7.35 (t, JZ7.1 Hz, 1H),
7.48 (td, JZ7.5, 1.5 Hz, 1H), 8.27 (dd, JZ7.5, 1.1 Hz, 1H);
13C NMR (100 MHz, CDCl3) d 22.1, 79.5, 81.6, 125.9,
132.1, 133.2, 133.7, 134.6, 140.8, 178.7 (C]O).
4.2.4. 1-(m-Tolyl)-2-propyn-1-ol.9 (1f, Table 3, entry 7)
Yellow oil; 1H NMR (400 MHz, CDCl3) d 2.37 (s, 3H), 2.37
(br s, 1H (OH)), 2.65 (d, JZ2.4 Hz, 1H), 5.41 (s, 1H), 7.15
(d, JZ7.3 Hz, 1H), 7.25–7.36 (m, 3H); 13C NMR
(100 MHz, CDCl3) d 21.4, 64.4, 74.7, 85.6, 123.6, 127.2,
128.5, 129.2, 138.3, 139.8.
4.4.2. 1-(2-Methoxyphenyl)-2-propyn-1-one.14 (2d, Table
3, entry 5) Yellow oil; 1H NMR (400 MHz, CDCl3) d 3.39
(s, 1H), 3.93 (s, 3H), 7.00–7.06 (m, 2H), 7.55 (ddd, JZ8.3,
7.3, 2.0 Hz, 1H), 8.06 (dd, JZ7.8, 2.0 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 55.8, 79.3, 82.1, 112.1, 120.1, 125.7,
133.1, 135.4, 159.9, 175.8 (C]O).
4.2.5. 1-(4-Chlorophenyl)-2-propyn-1-ol.10 (1g, Table 3,
entry 8) Yellow oil; 1H NMR (400 MHz, CDCl3) d 2.37 (d,
JZ2.4 Hz, 1H), 2.87 (br s, 1H (OH)), 5.40 (d, JZ2.4 Hz,
1H), 7.33 (dt, JZ8.3, 2.2 Hz, 2H), 7.45 (dt, JZ8.3, 2.2 Hz,
2H); 13C NMR (100 MHz, CDCl3) d 63.5, 75.1, 83.0, 127.8,
128.6, 134.2, 138.3.
4.4.3. 1-(3-Chlorophenyl)-2-propyn-1-one.15 (2e, Table 3,
entry 6) Orange oil; 1H NMR (400 MHz, CDCl3) d 3.49 (s,
1H), 7.45 (t, JZ7.8 Hz, 1H), 7.61 (ddd, JZ7.8, 2.0, 1.0 Hz,
1H), 8.04 (td, JZ7.8, 1.0 Hz, 1H), 8.12 (t, JZ2.0 Hz, 1H);
13C NMR (100 MHz, CDCl3) d 79.8, 81.5, 127.7, 129.5,
129.9, 134.3, 135.0, 137.4, 175.8 (C]O).
4.3. General procedure for the preparation of calcium
phosphate-vanadate apatite (CPVAP)
Calcium
phosphate-vanadate
apatite
(CPVAP)
Ca10(PO4)6Kx(VO4)x(OH)2 (xZ3.1) was prepared by fol-
lowing the method described by Boechat et al.7 To a
solution of Ca(NO3)2$4H2O (15.8 g, 66.7 mmol) in H2O
(60 mL) in a 500 mL three-necked round bottomed flask
was added a solution of VCl3 (8.6 g, 54.4 mmol) in H2O
(brown solution, 30 mL). The mixture was then brought to
pH 11–12 with 28% ammonia solution in H2O (dark brown
solution) and thereafter diluted to 120 mL. In a separate
flask, a solution of (NH4)2HPO4 (5.3 g, 40.0 mmol) in H2O
(100 mL) was brought to pH 11–12 with 28% ammonia
solution in H2O and then diluted to 160 mL. This
(NH4)2HPO4 solution was added dropwise from dropping
funnel to the above Ca(NO3)2/VCl3 solution with stirring for
30 min. After the addition, the mixture was heated to 95 8C
for 10 min. After cooling, it was filtered and the separated
solid was washed with water (20 mL!7). This solid was
dried at 80 8C for 15 h and calcined at 500 8C for 3 h to give
9.1 g of CPVAP as a pale brown solid. The vanadium
content in the CPVAP was 2.9 mmol gK1 estimated by ICP
atomic emission analysis.
4.4.4. 1-(m-Tolyl)-2-propyn-1-one.14 (2f, Table 3, entry
7) Yellow oil; H NMR (400 MHz, CDCl3) d 2.43 (s, 3H),
1
3.42 (s, 1H), 7.39 (t, JZ7.8 Hz, 1H), 7.45 (d, JZ7.8 Hz,
1H), 7.95 (s, 1H), 7.98 (d, JZ7.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d 21.3, 80.3, 80.5, 127.1, 128.5, 129.9,
135.2, 136.1, 138.5, 177.4 (C]O).
4.4.5. 1-(4-Chlorophenyl)-2-propyn-1-one.15 (2g, Table
3, entry 8) Orange solid; mp: 96.0–97.0 8C; 1H NMR
(400 MHz, CDCl3) d 3.47 (s, 1H), 7.48 (dt, JZ8.8, 2.0 Hz,
2H), 8.10 (dt, JZ8.8, 2.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3) d 79.9, 81.2, 129.0, 130.9, 134.4, 141.1, 175.9
(C]O).
4.5. General procedure for recycling of the catalyst
Recovered CPVAP by filtration from the former run of the
oxidation of porpargylic alcohols was washed with diethyl
ether and dried under vacuum at room temperature before
use for the next run.
Hydroxyapatite-supported vanadium, ruthenium and palla-
dium were prepared by treatment of hydroxyapatite
(HAP)12 with VCl3, RuCl3 and PdCl2(MeCN)2 at room
temperature in water or acetone by following the methods
described by Kaneda et al.3a,c,8
Acknowledgements
4.4. General procedure for the CPVAP-catalyzed
oxidation of porpargylic alcohols with molecular oxygen
We thank Professor Masashi Inoue and Dr. Shinji Iwamoto
(Kyoto University) for their help in ICP atomic emission
analysis to measure vanadium contents in CPVAP. The
financial support from Japan Science and Technology
Corporation (JST) is also acknowledged.
To a suspension of CPVAP (50 mg, 0.15 mmol as
vanadium) in benzonitrile or n-butyronitrile (1 mL) in a

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Y. Maeda et al. / Tetrahedron 60 (2004) 9031–9036
6750–6755. (c) Nishimura, T.; Kakiuchi, N.; Inoue, M.;
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