Na4H3[SiW9Al3(H2O)3O37]·12H2O/H2O: a new system for selective oxidation of alcohols with H2O2 as oxidant

Article abstract of DOI:10.1016/j.tet.2006.12.030

This work describes a catalytic system consisting of both Na₄H₃[SiW₉Al₃(H₂O)₃O₃₇]·12H₂O(SiW₉Al₃) and water as solvents (a?small quantity of organic solvents were used as co-solvent for a few substrates) that can be good for selective oxidation of alcohols to ketones (aldehydes) using 30% H₂O₂ without any phase-transfer catalyst under mild reaction conditions. The catalyst system allows easy product/catalyst separation. Under the given conditions, the secondary hydroxyl group was highly chemoselectively oxidized to the corresponding ketones in good yields in the presence of primary hydroxyl group within the same molecule, and hydroxides are selectively oxidized even in the presence of alkene. Benzylic alcohols were selectively oxidized to the corresponding benzaldehydes in good yields without over oxidation products in solvent-free conditions. Nitrogen, oxygen, sulfur-based moieties, at least for the cases where these atoms are not susceptible to oxidation, do not interfere with the catalytic alcohol oxidation.

Full text of DOI:10.1016/j.tet.2006.12.030

Tetrahedron 63 (2007) 1826–1832
Na H [SiW Al (H O) O ]$12H O/H O: a new system for
4
3
9
3
2
3 37
2
2
selective oxidation of alcohols with H O as oxidant
2
2
a,b
a
a
Jianmin Wang, Liang Yan, Guang Qian, Shunqing Li, Keli Yang,
a
a
a
Haitao Liu and Xiaolai Wang
a,
*
a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences,
Lanzhou 730000, China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100000, China
Received 7 June 2006; revised 12 December 2006; accepted 13 December 2006
Available online 8 January 2007
Abstract—This work describes a catalytic system consisting of both Na H [SiW Al (H O) O ]$12H O(SiW Al ) and water as solvents
2
4
3
9
3
2
3
37
9
3
(
tones (aldehydes) using 30% H without any phase-transfer catalyst under mild reaction conditions. The catalyst system allows easy prod-
a small quantity of organic solvents were used as co-solvent for a few substrates) that can be good for selective oxidation of alcohols to ke-
2 2
O
uct/catalyst separation. Under the given conditions, the secondary hydroxyl group was highly chemoselectively oxidized to the corresponding
ketones in good yields in the presence of primary hydroxyl group within the same molecule, and hydroxides are selectively oxidized even in
the presence of alkene. Benzylic alcohols were selectively oxidized to the corresponding benzaldehydes in good yields without over oxidation
products in solvent-free conditions. Nitrogen, oxygen, sulfur-based moieties, at least for the cases where these atoms are not susceptible to
oxidation, do not interfere with the catalytic alcohol oxidation.
Ó 2006 Elsevier Ltd. All rights reserved.
1. Introduction
and environment) or phase-transfer catalyst (affect prod-
ucts/catalyst separation).
The oxidation of alcohols to carbonyl compounds is one of
the most frequently used synthetic reactions in organic
chemistry and several methods covering a wide variety of
reagents have been developed for this important synthetic
Over the past decade, polyoxometalates have awoken inter-
est for catalytic oxidations, as they are inherently stable to
oxidation. Most notably, Venturello found that [CH (n-
3
1
transformation. In the synthesis of naturally occurring com-
C H ) ] PO [WO(O ) ] displayed a catalytic activity for
4
8
17 3 3
2 2 4
pounds, one usually faces the manipulation of compounds
containing several types of functional groups, and it is nec-
essary to selectively oxidize a single group (primary, second-
ary alcohol or double bond) within the same molecules.
Thus, selective transformation of hydroxyl group has been
a challenging target for synthetic chemists since it offers
an alternative to synthesis via selective protection and depro-
tection. Many oxidizing reagents are known to promote
selective oxidation of secondary alcohols in the presence
non-solvent oxidations, although much room was left for
improvement. Another especially interesting subclass of
polyoxometalates, which are ‘sandwich’ type compounds
has shown to be efficient for catalytic oxygen-tranfer reac-
1
1–15
10ꢀ
tions,
in monophasic systems,
highly active in biphasic alkene epoxidation and alcohol
e.g. [Fe(II) (PW O ) ] for alkene epoxidation
4 9
34 2
1
6
2ꢀ
[WZnMn(II) (ZnW O ) ]
34 2
2
9
1
7,18
oxidation with H O .
2
Although these polyoxometalate
2
compounds are active in above reaction systems, most of
them have disadvantages, for example, need of noxious
organic solvents.
2
,25d
of primary alcohols,
including halogen based oxidants.
In these readily available procedures, hydrogen peroxide is
an ideal oxidant that has attracted considerable attention
1
e,2c,3–9
in recent years.
procedures
There have been a number of
for alcohol oxidation using H O and in
In our early work, transition-metal substituent polyoxometa-
late Na [SiW ZnH O ]$12H O was synthesized and used
6
–10
2
2
6
11
2
40
2
1
9
situ generated or preformed metal complexes. However,
some of them still need further improvement for their appli-
cation in the practical organic synthesis. For instance, the
systems usually need toxic solvent (affect human health
as the catalyst for the oxidation of alcohols. The results
suggested that the catalyst Na [SiW ZnH O ]$12H O
6
11
2
40
2
had high catalytic activity. Herein, we report our investiga-
tion on the redox activity of non-transition-metal substituent
(tri-aluminum) polyoxometalate for oxidation of alcohols;
it is very efficient and selective catalyst for oxidation of
*
Corresponding author. E-mail: wangjianmin060102@yahoo.com.cn
0
040–4020/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.12.030

J. Wang et al. / Tetrahedron 63 (2007) 1826–1832
1827
alcohols with H O . The reaction can be carried out under
2
organic–aqueous biphasic conditions or organic–solvent-
free conditions.
Table 2. Oxidation of alcohols with hydrogen peroxide catalyzed by
SiW Al in acetonitrile or without solvent
2
9
3
Entry
1
Substrates
Solvent
—
Time
7
Products (yield %)
OH
O
(99)
2
. Results and discussion
OH
OH
O
a
2
—
7
8
(97)
2
.1. Effect of catalyst on the oxidation of cyclohexanol
O
Initially, oxidation of cyclohexanol was used as the model
reaction to test the activity of various catalysts. The results
were shown in Table 1, which were obtained after 7 h of
reactions using 2 mmol of the catalysts (SiW Al , SiW Ga ,
SiW In , and SiW Tl ), 17 mmol of cyclohexanol, and
3
3
SiW Al was the best catalyst for the reaction, and cyclohex-
anol was completely consumed after 7-h reaction with exclu-
sive selectivity to cyclohexanone. Other catalysts were also
capable of catalyzing the model reaction, but their efficien-
cies seemed to be slightly inferior compared with SiW Al .
Compared with other polyoxometalate catalysts, the cata-
lytic system does not need phase-transfer catalyst; this could
be due to amphoteric element Al (or Zn) introduced into
polyoxometalate that changes distribution of charges in the
pattern different to other transition-metal substituent poly-
oxometalate catalysts, and changes its redox in reaction
system. SiW Al was, therefore, chosen as a catalyst for
3
4
5
—
(99)
OH
O
9
3
9
3
—
7
(99)
9
3
9
0 mmol of 30% aqueous H O . It was observed that
2 2
OH
O
9
3
Acetonitrile
—
9
(99)
O
6
7
OH
10
(78)
OH
OH
9
3
2
0
OH Acetonitrile 12
(61)
O
Reaction conditions: 17 mmol of substrate, 2 mmol of catalyst, and 50 mmol
ꢁ
2 2
of H O (30%); temperature: 90 C; time: 7–12 h.
a
The fifth run.
9
3
2
.3. Selective oxidation of diols and enols
further investigation.
The results of oxidation for a variety of diols and enols using
H O as oxidant are given in Table 3. The observed transfor-
2
.2. Reaction of different monofunctional alcohols
2
2
mations were chemoselective when both the primary and
secondary hydroxyl groups were present within the same
molecules (Table 3). The ketones with the primary alcohol
untouched were obtained in good yields. For instance, 2-
ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and
A series of alcohols was then reacted by using this remark-
ably simple procedure and the results are presented in Table
2
. The secondary alcohols were all oxidized directly to the
corresponding ketones using the catalyst in a short time
with excellent yield and selectivity under the solvent-free
conditions. Actually, we found that there was no need for
phase-transfer reagent, as in the solvent-free oxidations
1,2-octanediol were all rather effectively oxidized to 1-hy-
droxy-ketone without the formation of byproducts. In these
cases, some lactones (five- or six-membered ring lactone)
were also formed as minor products. For instance, 1,4-pen-
tanediol, 1,5-hexanediol, and 1,7-octanediol were oxidized
to 1-hydroxy-4-pentanone, 1-hydroxy-5-hexanone, and
8
,21
previously described.
Primary alcohols, for short-chain
alcohols, were oxidized to the corresponding organic acid
without acetonitrile, and for long-chain alcohols, an ounce
of acetonitrile was needed. When reactions were carried
out without any organic solvent with long-chain alcohols
as substrates, longer time was needed to achieve good yields
1-hydroxy-7-octanone with a little lactones in the obtained
products. The result indicated that the catalytic system was
highly active in selective oxidation of the compounds with
both primary and secondary hydroxyl moieties. Trost and
(Table 2). The same investigation was observed in the
solvent-free system described by Noyori.
8
2
2
Masuyama found the same selectivity in a molybdenum
catalyzed alcohol oxidation by hydrogen peroxide. Alke-
nols, for instance, 3-octen-2-ol, 1-dodecen-3-ol, and 10-un-
decen-3-ol were all efficiently oxidized to the corresponding
alkenones (alkene aldehyde) in high yields. Allylic alkenols
Table 1. Oxidation reaction of cyclohexanol to cyclohexanone with hydro-
gen peroxide as an oxidant and without solvent
a
Entry
Catalyst
SiW12
Product (yield %)
(
reactions at low temperature) were more reactive than non-
1
2
3
4
5
6
7
8
9
0
0
100
62
0
27
33
18
0
ꢁ
allylic alkenols (reactions at 60 C). It was worth noting that
no epoxide of alkenol was detected in alkenol oxidations. It
showed that the catalyst was highly active and selective for
oxidation of diols and enols.
SiW
SiW
SiW
—
9
9
9
Al
Al
3
b
3
SiW
SiW
SiW
9
9
9
Ga
In
Tl
3
3
2.4. Selective oxidation of benzylic alcohols and
heterocyclo compounds
3
AlCl
3
10
Al(NO
3
)
3
0
a
ꢁ
Benzylic alcohols were selectively oxidized to the corre-
sponding benzaldehydes in moderate to good yields without
over oxidation under solvent-free conditions. Likewise,
Reactions were carried out with 17 mmol of the alcohol at 90 C, with
mmol of catalysts, and 30 mmol of 30% aqueous H for 7 h.
Catalysts (1 mmol).
2
2 2
O
b

1
828
J. Wang et al. / Tetrahedron 63 (2007) 1826–1832
catalyzed by SiW Al in acetonitrile or without solvent
Table 3. The selective oxidation of alcohols with H
2
O
2
9
3
ꢁ
Substrate
OH
H
2
O
2
(mmol)
Solvent
Temp ( C)
Time (h)
Conv. (%)
Product (select. %)
O
5
5
5
5
0
0
0
0
—
90
9
100
(99)
OH
OH
OH
O
—
—
—
90
90
90
7
9
9
100
100
100
(99)
(99)
OH
OH
OH
OH
OH
O
OH
O
(99)
OH
OH
O
(
62)
OH
OH
5
0
—
90
9
100
OH
OH
(
37)
O
O
(
63)
OH
OH
OH
5
0
—
90
9
100
OH
HO
O
(
35)
O
5
4
0
0
—
—
90
70
9
7
100
100
(99)
OH
OH
OH
O
(92)
3
3
0
0
Acetonitrile
Acetonitrile
60
60
5
7
100
100
(89)
OH
OH
O
O
(76)
5
0
Acetonitrile
90
9
100
(99)
OH
O
ꢁ
Reaction condition: substrate 20 mmol, catalyst 1.7 mmol, temperature 60–95 C, and 30–50 mmol of 30% solution of H
2
O
2
.
furfurol, thiophene-2-methanol, and pyridine-2-methanol
were oxidized to furfural, 2-thiophenecarboxaldehyde, and
monofunctional alcohols oxidation. Furthermore, secondary
alcohols are selectively oxidized even in the presence of
primary ones and hydroxides are selectively oxidized even
in the presence of alkene. This may be due to amphoteric
element Al (or Zn) introduced into polyoxometalate that
changes distribution of charges in the pattern different to
other transition-metal substituent polyoxometalate com-
pound catalysts. The important advantage of this method,
besides the organic-solvent-free conditions for most of sub-
strates, is that it does not require a phase-transfer catalyst.
In addition, the catalytic system offers the advantages of
simplified workup procedure and recycling.
2
-pyridinecarboxaldehyde in high yields, respectively. No
oxidation was observed at the N-atom of pyridine-2-metha-
nol and S-atom of thiophene-2-methanol (Table 4).
3. Conclusions
In conclusion, organic-solvent-free oxidations of alcohols
using aqueous hydrogen peroxide as an oxidant and SiW Al3
as catalyst provides a general, safe, and simple method for
9

J. Wang et al. / Tetrahedron 63 (2007) 1826–1832
1829
Table 4. The selective oxidation of alcohols with H
Substrate (mmol)
2
O
2
catalyzed by SiW
9
3
Al in acetonitrile or without solvent
ꢁ
H
2
O
2
Solvent
Temp ( C)
Time (h)
Conv. (%)
Product (select. %)
OH
O
3
3
3
3
3
3
3
0
0
0
0
0
0
0
—
90
6
100
100
100
100
74
(99)
CH O
CH O
3
3
OH
O
(99)
—
—
—
—
—
—
90
90
90
90
90
90
7
5
OH
O
(99)
OH
O
6
(99)
Cl
Cl
OH
O
12
5
(99)
O N
O2N
2
OH
O
100
100
(99)
(99)
N
N
O
S
O
S
2
OH
O
3
0
—
90
4
100
(99)
OH
O
ꢁ
Reaction condition: substrate 20 mmol, catalyst 1.7 mmol, temperature 60–95 C, and 30–50 mmol of 30% solution of H
2
O
2
.
ꢁ
4
. Experimental
in 120 ml hot water (90 C) was added in small portions 5.7 g
(22.7 mmol) of solid Al(NO ) $9H O. The pH of the mixture
was adjusted to 5 with sodium carbonate and kept at the tem-
3 3 2
4
.1. General
ꢁ
its volume of cold methanol was added to the cold filtrate
(5 C). The precipitated white salt was filtered off. The ob-
perature (90 C) for 30 min, then cooled, and filtered. Twice
1
13
H and C NMR spectra were measured on a JEOL JNM-
A400 NMR spectrometer at 400 and 100 MHz, respectively.
The chemical shifts of H NMR spectra are reported in parts
per million on d scale downfield from tetramethysilane used
as an internal standard and signal patterns are indicated as
follows: s, singlet; d, doublet; t, triplet; q, quartet; m, multi-
plet; br, broad peak. The chemical shifts of C NMR spectra
are reported in parts per million with chloroform-d as an in-
ternal standard. Gas chromatographic analyses were carried
out using an Agilent6890N/5973N/GC–MS (column: HP-1
ꢁ
1
tained solid was washed with a 2:1 (v/v) methanol/water
mixture, and recrystallized three times with warm water (50–
ꢁ
the powder was confirmed as Na H [SiW Al (H O) O ]$
60 C). After filtering, the salt was air-dried. The structure of
4
3
9
3
2
3 37
1
3
12H O from IR and UV spectroscopic data and elemental
2
analysis (Figs. 1 and 2). Purities of all prepared catalysts
were ꢃ98% according to the analysis.
1
00% dimethylpolysiloxane 30 mmꢂ320 mmꢂ0.25 mm)
and a PE-XL Autosystem equipped with an FID detector
carrier¼He (constant flow, 2.2 ml/min); mode¼split (split
1
00
during reaction
before reaction
after reaction
(
9
8
7
6
5
4
3
0
0
0
0
0
0
0
ꢁ
ꢁ
ratio¼80:1); injector T¼250 C; detector (FID) T¼280 C).
.2. Materials and reagents
4
All organic reagents (purchased from Fluck) were used di-
rectly. Na WO $2H O, NaSiO $9H O, Al(NO ) , Ga(NO ) ,
In(NO ) , and Tl(NO ) were purchased from Beijing Chem-
3
2
4
2
4
2
3 3
3 3
3
3 3
ical Reagent Co.
.3. Catalysts preparation and analysis
Na HSiW O $13H O was prepared according to previous
4
9
9
34
2
2
3
20
4
method. The synthesis of the catalyst Na H [SiW Al -
9
(H O) O ]$12H O polyoxometalate was proceeded accord-
2 3 37 2
ing to previous literature and made some redresser: to a
4
3
3
00
500
600
700
800
900
1000
1100
wavenumber (cm-1)
2
4
stirred solution of 21 g (7.6 mmol) of Na HSiW O $13H O
9
9 3
Figure 1. IR spectra of catalyst SiW Al before, during, and after reaction.
9
34
2

1830
J. Wang et al. / Tetrahedron 63 (2007) 1826–1832
was stirred at desired temperature for 30 min, and then
0
1
0
0
0
0
0
.0
.8
.6
.4
.2
.0
.02 mol (2 ml) cyclohexanol was added. The biphasic mix-
ꢁ
a
b
ture was stirred at 90 C for 9 h. After the reaction, the
organic phase was separated, washed with 2 ml Na S O ,
and distilled to gain the product. Spectral data of each prod-
2
2 3
2
5
uct were compared with the literature values. The catalyst
during and after reaction was characterized by IR and UV–
vis, and spectroscopic data indicated that the catalyst is
stable for the selective oxidation of alcohols (Figs. 1 and 2).
1
4
.5.1.1. Cyclohexanone. H NMR (400 MHz, CDCl )
3
1
3
d 1.65–2.1 (m, 6H), 2.4–2.5 (m, 4H); C NMR d 26.0,
8.1, 42.0, 212.7.
2
2
00
400
600
1
4
.5.1.2. Cyclopentanone. H NMR (400 MHz, CDCl )
3
wavenumber (nm)
13
d 1.75–2.25 (m, 4H), 2.26–2.36 (m, 4H); C NMR d 24.3,
7.6, 217.47.
3
Figure 2. UV–vis spectra of catalyst: (a) before reaction and (b) during
reaction.
1
4.5.1.3. 2-Butanone.
H NMR (400 MHz, CDCl3)
d 1.02–1.07 (m, 3H), 1.8–2.3 (m, 2H), 2.40–2.49 (m, 3H);
C NMR d 7.65, 29.5, 37.2, 210.1.
1
3
4.3.1. Data of analysis. Thermogravimetric analysis indi-
cated that there were 15 water molecules per heteropoly
compound (Na H [SiW Al (H O) O ]$12H O) and the re-
37
sults of elemental analysis in % (w/w) were: Si 1.00 (1.03),
W 60.89 (60.84), Al 2.98 (2.98), Na 3.38 (3.37), H 0.10
0.10), O 21.71 (21.75), H O 9.94 (9.92) found (calculated).
2
1
4.5.1.4. Octan-2-one. H NMR (400 MHz, CDCl
d 0.81–0.89 (m, 3H), 1.15–1.40 (m, 6H), 1.50–1.54 (m,
)
4
3
9
3
2
3
2
3
1
3
2H), 2.10 (s, 3H), 2.39 (t, 2H, J¼7.4 Hz); C NMR d 14.0
(
(q), 22.5 (t), 23.9 (t), 29.0 (t), 29.7 (q), 31.7 (t), 43.7 (t),
2
08.7 (s).
4
.4. General procedure for oxidation of alcohols
1
4.5.1.5. n-Hexanoic acid. H NMR (400 MHz, CDCl )
d 0.81–0.84 (m, 3H), 1.29–1.7 (m, 6H), 2.31–2.33 (m,
3
A 25-ml round bottomed flask with 2 ml of CH CN (or
3
solvent-free) equipped with a magnetic stirrer and reflux
condenser was charged with 0.1 g (1.7 mmol) catalyst and
1
3
2H), 11.66 (s, 1H); C NMR d 13.79, 22.35, 24.47, 31.34,
34.21, 180.7.
0
.04 mol (2.7 ml) aqueous hydrogen peroxide (30%). The
1
mixture was stirred at desired temperature for 30 min, and
then 0.02 mol (2 ml) alcohol was added. The biphasic
mixture was stirred at 90 C for 9 h. After the reaction, the
mixture was treated with a 10% sodium hydrogen sulfite
solution to decompose the unreacted hydrogen peroxide
and then with 10% sodium hydroxide. The product was
extracted with n-butyl-ether. The pure product was obtained
by distillation or silica gel column chromatography (hexane/
ethyl acetate, 10–20/1). Spectral data of each product were
4.5.1.6. Octanoic acid. H NMR (400 MHz, CDCl3)
d 0.88 (t, 3H, J¼7.1 Hz), 1.21–1.38 (m, 11H), 1.59–1.67
ꢁ
13
(m, 2H), 2.32–2.37 (m, 1H), 4.12 (q, 2H, J¼7.5 Hz); C
NMR d 14.05, 14.24, 22.58, 24.90, 29.05, 29.08, 31.64,
34.38, 176.95.
1
4.5.1.7. 2-Ethyl-1,3-hexanediol. H NMR (400 MHz,
CDCl ) d 0.80–1.05 (m, 6H), 1.4–1.70 (m, 4H), 2.20–2.82
3
1
3
(m, 1H, J¼6.5 Hz), 3.68 (2H, d); C NMR d 11.8, 13.8,
2
1,25
compared with the literature values.
16.8, 21.5, 45.2, 55.7, 62.9, 215.2.
1
4.5. Procedure for oxidation of cyclohexanol and reusing
of the catalyst
4.5.1.8. 1-Hydroxy-2,2,4-trimethyl-3-pentanone.
H
NMR (400 MHz, CDCl ) d 1.07 (d, 6H, J¼6.4 Hz), 1.18
3
(
s, 6H), 2.55 (br d, 1H, J¼7.4 Hz), 3.25–2.80 (m, 1H),
1
3
A 25-ml round bottomed flask equipped with a magnetic stir-
rer and reflux condenser was charged with 0.1 g (1.7 mmol)
catalyst and 0.04 mol (2.7 ml) aqueous hydrogen peroxide
3.52 (s, 2H); C NMR d 19.8, 21.0, 34.5, 49.6, 69.3, 221.5.
1
4.5.1.9. 1-Hydroxyoctan-2-one. H NMR (400 MHz,
CDCl ) d 4.22 (s, 2H), 3.14 (s, 1H), 2.37 (t, 2H,
(
3
30%). The mixture was stirred at desired temperature for
0 min, and then 0.02 mol (2 ml) cyclohexanol was added.
3
J¼6.9 Hz), 1.61–1.63 (m, 2H), 1.25–1.35 (m, 6H,), 0.85 (t,
ꢁ
13
The mixture was stirred at 90 C for 9 h. After the reaction,
the organic phase was separated, washed with 2 ml Na S O ,
3H, J¼7.0 Hz); C NMR d 14.1, 22.5, 23.8, 28.9, 31.5,
38.5, 68.2, 210.0.
2
2 3
and distilled to gain the product. Spectral data of each prod-
uct were compared with the literature values.
1
4.5.1.10. 3-Hydroxymethyl-cyclopentanone. H NMR
400 MHz, CDCl ) d 1.63–1.85 (m, 7H), 2.83 (s, 1H), 3.76
(
3
1
3
4
.5.1. The 2–5 run. A 25-ml round bottomed flask equipped
(2H, d, J¼6.3 Hz); C NMR d 25.5, 38.0, 38.9, 42.1,
with a magnetic stirrer and reflux condenser was charged
with the aqueous phase of the last run containing the poly-
oxometalate catalyst 0.1 g (1.7 mmol), distillation residue of
the last run containing some polyoxometalate catalyst, and
64.9, 220.1.
1
4.5.1.11. 6-Hydroxy-2-hexanone. H NMR (400 MHz,
CDCl ) d 1.30–1.32 (m, 1H), 2.55–1.96 (m, 5H), 3.67 (s,
2H); C NMR d 23.5, 31.3, 42.1, 42.7, 62.1, 211.6.
3
1
3
0
.04 mol (2.7 ml) hydrogen peroxide (30%). The mixture

J. Wang et al. / Tetrahedron 63 (2007) 1826–1832
1831
1
1
4
.5.1.12.
5-Hydroxy-2-pentanone.
H
NMR
400 MHz, CDCl ) d 1.26–1.28 (m, 1H), 1.66–2.00 (m,
2
4.5.1.24. 2-Thiophenecarboxaldehyde.
H
NMR
(400 MHz, CDCl ) d 7.0–7.3 (m, 1H), 7.6–7.9 (m, 2H),
(
3
3
1
3
13
H), 2.55–2.30 (m, 4H), 3.64 (t, 2H, J¼6.3 Hz); C NMR
10.1 (s, 1H); C NMR d 128.6, 135.4, 136.7, 144.1, 183.1.
d 26.4, 28.8, 39.4, 61.9, 212.1.
.5.1.13. 1-Hydroxyoctan-7-one. H NMR (400 MHz,
1
References and notes
4
CDCl ) d 0.85 (t, 3H, J¼6.8 Hz), 1.21–1.38 (m, 6H), 1.61
3
1
. (a) Hudlicky, M. Oxidation in Organic Chemistry; American
Chemical Society: Washington, DC, 1990; (b) Comprehensive
Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon:
Oxford, 1991; (c) Luzzio, F. A. Org. React. 1998, 53, 1–221;
(d) Katritzky, A. R.; Meth-Cohn, O.; Rees, C. W.; Pattenden,
G.; Moody, C. J. Comprehensive Organic Functional Group
Transformations; Elsevier Science: Oxford, 1995; Vols. 3 and
(
m, 2H), 2.37 (t, 2H, J¼7.6 Hz), 3.14 (s, 1H), 4.21 (s,
1
3
2
6
H); C NMR d 14.1, 22.5, 23.8, 28.9, 31.5, 38.5,
8.2, 210.0.
1
4.5.1.14. 2-Cyclohexen-1-one. H NMR (400 MHz,
CDCl ) d 2.36–2.40 (m, 2H), 2.50–2.59 (m, 2H), 6.13 (1H,
3
1
3
dt, J¼4.2, 2 Hz), 7.45 (1H, dd, J¼8.1, 2.8 Hz); C NMR
5
1
; (e) Noyori, R.; Aoki, M.; Sato, K. Chem. Commun. 2003,
977–1986.
d 22.79, 25.72, 38.13, 129.84, 150.86, 199.65.
2
. (a) Arterburn, J. B. Tetrahedron 2001, 57, 9765–9788; (b)
Gogoi, P.; Kumar, G.; Konwar, D. J. Org. Chem. 2004, 69,
1
4
.5.1.15. 3-Octen-2-one. H NMR (400 MHz, CDCl3)
d 0.90 (t, 3H, J¼7.6 Hz), 1.20–1.80 (4H, m), 2.23 (2H, m),
5153–5154; (c) Xi, Z. W.; Zhou, N.; Sun, Y.; Li, K. L.
Science 2001, 292, 1139–1141.
2
.30 (s, 3H), 6.00 (d, 1H, J¼16.6 Hz), 6.71 (dt, 1H,
1
3
J¼16.5, 7.0 Hz); C NMR d 13.9, 21.88, 27.12, 30.28,
3
4
. Sato, K.; Aokil, M.; Noyori, R. Science 1998, 281, 1646–1647.
. Deng, Y. Q.; Ma, Z. F.; Wang, K.; Chen, J. Green Chem. 1999,
3
2.17, 132.13, 148.65, 201.14.
1
, 275–276.
1
4
CDCl ) d 1.2–1.40 (m, 10H), 1.50–1.62 (m, 2H), 2.02 (m,
.5.1.16. 11-Dodecen-2-one.
H NMR (400 MHz,
5
. Guo, M. L. Chin. J. Catal. 2003, 24, 483–484.
6. Indira, V.; Joy, P. A.; Gopinathan, S. C.; Gopinathan. Indian J.
Chem. Sect. A 1998, 37, 261–267.
3
2
2
H), 2.14 (s, 3H), 2.42 (t, 2H, J¼6.9 Hz), 4.90–5.02 (m,
1
3
H), 5.80 (tdd, 1H, J¼6.8, 10.6, 16.9 Hz); C NMR
7
. Wei, J. F.; Shi, X. Y.; He, D. P.; Zhang, M. Chin. Sci. Bull. 2002,
7, 1628–1630.
. Sato, K.; Aokil, M.; Takagi, J.; Noyori, R. J. Am. Chem. Soc.
997, 119, 12386–12387.
d 23.8, 29.0, 29.13, 29.26, 29.31, 29.80, 33.75, 43.78,
14.12, 138.76, 210.11.
4
1
8
1
1
4
.5.1.17. 1-Dodecen-3-one.
H NMR (400 MHz,
9. Manyar, H. G.; Chaure, G. S.; Kaman, A. Green Chem. 2006, 4,
344–346.
10. Zhou, M. J.; Wei, Ch. P.; Bi, Y. L.; Zhen, K. J. Chin. J. Catal.
1999, 20, 437–441.
11. Hill, C. L.; Brown, R. B., Jr. J. Am. Chem. Soc. 1986, 108,
536–538.
CDCl ) d 0.91 (t, 3H, J¼7.1 Hz), 1.20–1.40 (m, 12H),
3
1
.50–1.70 (m, 2H), 2.61 (t, 2H, J¼7.6 Hz), 5.85 (dd, 1H,
J¼1.6, 10.9 Hz), 6.20 (dd, 1H, J¼1.6, 18.1 Hz), 6.41 (dd,
1
3
1
2
H, J¼10.9, 19.6 Hz); C NMR d 14.07, 22.63, 24.00,
9.25, 29.40, 31.85, 39.85, 127.81, 136.60, 200.98.
1
2. Loose, I.; B €o sing, M.; Klein, R.; Krebs, B.; Schulz, R. P.;
Scharbert, B. Inorg. Chim. Acta 1997, 263, 99–108.
13. Hill, C. L.; Zhang, X. Nature 1995, 373, 324–325.
1
4
.5.1.18. Benzaldehyde. H NMR (400 MHz, CDCl )
3
1
3
d 7.45–7.85 (m, 5H), 10.01 (s, 1H); C NMR d 128.8,
29.5, 134.3, 136.2, 192.2.
1
14. Zhang, X.; Sasaki, K.; Hill, C. L. J. Am. Chem. Soc. 1996, 118,
4
809–4816.
15. Neumann, R.; Abu-Gnim, C. J. Am. Chem. Soc. 1990, 112,
025–6031.
16. Khenkin, A. M.;Hill, C. L. MendeleevCommun. 1993, 140–141.
7. Neumann, R.; Gara, M. J. Am. Chem. Soc. 1994, I16, 5509–
510.
1
4
.5.1.19. 4-Methoxybenzaldehyde. H NMR (400 MHz,
6
CDCl ) d 3.86 (s, 3H), 6.95 (d, 2H, J¼8.6 Hz), 7.85 (d, 2H,
3
1
3
J¼8.4 Hz), 10.08 (s, 1H); C NMR d 55.4, 114.1, 129.7,
31.8, 164.4, 190.6.
1
1
5
1
18. Gara, M. J. Am. Chem. Soc. 1995, 117, 5066–5074.
19. Wang, J.; Yan, L.; Li, G.; Wang, X.; Ding, Y.; Suo, J.
Tetrahedron Lett. 2005, 46, 7023–7027.
4
.5.1.20. 4-Chlorobenzaldehyde. H NMR (400 MHz,
CDCl ) d 7.71–7.75 (m, 4H), 10.02 (s, 1H); C NMR
1
3
3
d 129.2, 130.5, 131.9, 134.7, 190.3.
2
0. (a) Ishii, Y.; Yamawaki, K.; Ura, T.; Yamada, H.; Yoshida, T.;
Ogawa, M. J. Org. Chem. 1988, 53, 3587–3593; (b)
Ventuello, C.; Alneri, E.; Ricci, M. J. Org. Chem. 1983, 48,
1
4
.5.1.21. 4-Nitrobenzaldehyde. H NMR (400 MHz,
CDCl ) d 8.10 (d, 2H, J¼8.1 Hz), 8.3 (d, 2H, J¼7.9 Hz),
3
3
831–3833; (c) Bortolini, O.; Furia, F. D.; Modena, G.;
1
3
1
0.3 (s, 1H); C NMR d 124.2, 130.5, 139.9, 151.0, 190.2.
Seraglia, R. J. Org. Chem. 1985, 50, 2688–2690.
1. Bogdal, D.; qukasiewicz, M. Synlett 2000, 143–145.
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2
2
1
4
.5.1.22. 2-Pyridinecarboxaldehyde.
400 MHz, CDCl ) d 7.5–7.6 (m, 1H), 7.8–8.0 (m, 2H),
3
.8–9.0 (m, 1H), 10.1 (s, 1H); C NMR d 193.3, 152.7,
50.2, 137.2, 127.8, 121.9.
H
NMR
(
8
1
1
3
2
2
3. Herve, G.; Teze, A. Inorg. Chem. 1977, 16, 2115–2117.
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6
02–604.
1
4.5.1.23. Furfural. H NMR (400 MHz, CDCl ) d 6.6
s, 1H), 7.4 (s, 1H), 7.8 (s, 1H), 9.7 (s, 1H); C NMR
25. (a) Simoms, W. W.; Zanger, M. The Sadtler Guide to NMR
Spectra; Sadtler Research Laboratories: Philadelphia, PA,
1972; (b) Pouchert, C. J.; Campbell, J. R. The Aldrich
3
1
3
(
d 112.6, 121.1, 148.1, 153.0, 178.8.

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