Allyltriphenylphosphonium Peroxodisulfate (CH2=CHCH 2PPh3)2S2O8: An Efficient and Convenient Reagent for the Oxidation of Alcohols and Silyl and THP-Ethers under Nonaqueous Conditions

Article abstract of DOI:10.1081/SCC-120030303

The preparation of allyltriphenylphosphonium peroxodisulfate (ATPPD) as a new and efficient reagent for the oxidation of primary and secondary alcohols, trimethylsilyl and tetrahydropyranyl (THP) ethers to their corresponding carbonyl compounds in refluxing acetonitrile with 1.1:1 molar equivalents of the oxidant is described.

Full text of DOI:10.1081/SCC-120030303

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Allyltriphenylphosphonium Peroxodisulfate
(
CH ˭CHCH PPh ) S O : An Efficient and Convenient
2 2 3 2 2 8
Reagent for the Oxidation of Alcohols and Silyl and
THP‐Ethers Under Nonaqueous Conditions
a
a
a
M. Tajbakhsh , M. M. Lakouraj & A. Fadavi
a
Department of Chemistry, Faculty of Science , University of Mazandaran , Babolsar,
7415, Iran
4
Published online: 21 Aug 2006.
To cite this article: M. Tajbakhsh , M. M. Lakouraj & A. Fadavi (2004) Allyltriphenylphosphonium Peroxodisulfate
(
CH ˭CHCH PPh ) S O : An Efficient and Convenient Reagent for the Oxidation of Alcohols and Silyl and THP‐Ethers Under
2 2 3 2 2 8
Nonaqueous Conditions, Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 34:7, 1173-1181, DOI: 10.1081/SCC-120030303
To link to this article: http://dx.doi.org/10.1081/SCC-120030303
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w
SYNTHETIC COMMUNICATIONS
Vol. 34, No. 7, pp. 1173–1181, 2004
Allyltriphenylphosphonium Peroxodisulfate
(CH 55CHCH PPh ) S O :AnEfficientand
2 2 3 2 2 8
Convenient Reagent for the Oxidation of
Alcohols and Silyl and THP-Ethers
Under Nonaqueous Conditions
M. Tajbakhsh,* M. M. Lakouraj,* and A. Fadavi
Department of Chemistry, Faculty of Science,
University of Mazandaran, Babolsar, Iran
ABSTRACT
The preparation of allyltriphenylphosphonium peroxodisulfate (ATPPD)
as a new and efficient reagent for the oxidation of primary and secondary
alcohols, trimethylsilyl and tetrahydropyranyl (THP) ethers to their corre-
sponding carbonyl compounds in refluxing acetonitrile with 1.1 : 1 molar
equivalents of the oxidant is described.
Key Words: Oxidation; Allyltriphenylphosphonium peroxodisulfate;
Trimethylsilyl ethers; Tetrahydropyranyl ethers.
*
Correspondence: M. Tajbakhsh and M. M. Lakouraj, Department of Chemistry,
Faculty of Science, University of Mazandaran, Babolsar 47415, Iran; E-mails:
tajbaksh@umz.ac.ir/lakouraj@umz.ac.ir.
1
173
DOI: 10.1081/SCC-120030303
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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1
174
Tajbakhsh, Lakouraj, and Fadavi
INTRODUCTION
The peroxodisulfate ion is one of the strongest oxidizing agent. The inves-
[
1]
tigations on application of peroxidisulfate ion in organic synthesis as an
oxidant were performed in aqueous acidic or basic solution or in the presence
of transition metal ions. In recent decades much attention has been given to
the synthesis and application of new peroxodisulfate compounds such as
[2]
tetrakis(pyridine)silver(II) peroxodisulfate, tetrabutylammonium peroxodi-
[
3]
[4]
sulfate, benzyltriphenyl-phosphonium peroxodisulfate, and bis(1-benzyl-
3
,5,7-1-azoniatricyclo-[3.3.1.1 ]decane) peroxodisulfate which were used
,7
[5]
3
for the oxidation of organic compounds under nonaqueous conditions.
The protection of functional group is an important process in the synthesis of
[
6]
complex organic molecules. Alcohols are typically very reactive due to their
acidity,andareoftenprotectedfororganicsynthesis. Onewaytoprotecthydroxyl
group is to convert it to the corresponding silylether. Direct oxidation of tri-
methylsilyl ethers to the corresponding carbonyl compounds has found consider-
[
7–18]
able attention during recent years.
show limitations such as the requirement for aqueous reaction condition,
However, some of the reported methods
[8,11]
use
low yields of the pro-
Therefore, introduction of new methods and
[
13,17,18]
[10,12]
of expensive reagents,
[
long reaction time,
16]
[11]
ducts,
and tedious workup.
inexpensive reagents for such functional group transformation is still in demand.
On the other hand, tetrahydropyranyl (THP) group is one of the most
[6,19]
frequently used groups to protect alcohols and phenols.
Owing to the
outstanding stability of THP ether towards strongly basic media, organometal-
lic reagents, reductive and oxidative compounds, 3,4,-dihydro-2H-pyrane is
still a reagent of choice for protection of the alcohol group in peptide, nucleo-
tide, and carbohydrate chemistry. Since direct transformation of THP ethers to
[20–25]
their carbonyl compounds is rare in the literature,
method is desirable.
introduction of new
RESULTS AND DISCUSSION
In this communication we wish to report that allyltriphenylphosphonium
peroxodisulfate (ATPPD) a stable white solid is able to perform oxidation of
alcohols, THP and trimethylsilyl ethers in acetonitrile at reflux temperature.
This reagent is easily prepared from an aqueous solution of allyltriphenylphos-
[
26]
phonium bromide
and potassium peroxodisulfate at room temperature.
This oxidant is soluble in acetonitrile, DMSO, DMF and slightly soluble in
acetone and insoluble in carbon tetrachloride, dichloromethane, chloroform,
and ether. Structure of this reagent was confirmed by NMR, IR spectroscopy,
and elemental analysis.

ORDER
REPRINTS
Oxidation of Alcohols and Silyl and THP-Ethers with ATPPD
1175
A wide variety of primary and secondary benzylic alcohols oxidized to
the corresponding carbonyl compounds using ATPPD in refluxing acetonitrile
with 1.15 : 1 molar ratio of oxidant to substrate in high yields (Table 1, entries
1
–11). Under the same reaction conditions allylic alcohol has been selectively
oxidized to its a,b-unsaturated carbonyl compound without any cleavage of
the carbon–carbon double bond (Table 1, entry 12). a-Hydroxy ketone has
been converted to its a-diketone in moderate yield (Table 1, entry 15), even
on longer periods.
A noteworthy advantage of this reagent lies in its ability to selective oxi-
dation of benzylic hydroxyl group in the presence of aliphatic hydroxyl group.
In order to evaluate the selectivity of this reagent, the following competitive
reaction was carried out [Eq. (1)].
ATPPD
Ph2CHOH þ Cyclohexanol ƒƒƒƒƒƒƒƒƒƒ ƒƒ ! Ph2CO þ Cyclohexanol
CH3CN=Refluxð20 minÞ
ð95%Þ
ðunchangedÞ
ð1Þ
Table 1. Oxidation of alcohols with ATPPD in refluxing CH CN.
3
b
Time
(min)
Yield
(%)
a
Entry
Substrate
OH
p-ClC H CH OH
Product
1
2
3
4
5
6
7
8
9
C
6
H
5
CH
2
C
p-ClC H CHO
6
H
5
CHO
20
15
20
20
20
15
20
20
30
20
30
35
40
60
60
60
60
60
95
84
86
94
92
92
91
95
87
83
81
86
80
30
50
—
—
—
6
4
2
6
4
o-ClC
p-CH
6
H
4
CH
2
OH
OH
o-ClC
p-CH
6
H
4
CHO
CHO
3
C
6
H
4
CH
2
3
C
6
H
4
o-CH C H CH OH
o-CH C H CHO
3
3
3
6
4
2
3
3
3
6
4
p-CH
o-CH
OC
OC
6
H
4
CH
2
2
OH
OH
p-CH
o-CH
OC
OC
6
H
4
CHO
CHO
6
H
4
CH
6
H
4
(C H ) CHOH
6 5 2
(C H ) CO
6 5 2
p-ClC
CH(OH)CH
p-ClC H CH(OH)CH
6
H
4
CH(OH)C
6
H
5
p-ClC
COCH
p-ClC H COCH
3
6 4 6 5
H COC H
10
11
12
13
14
15
16
17
18
C
6
H
5
3
C
6
H
5
3
6
4
3
6
4
C H CH 55 CHCH OH
C H CH 55 CHCHO
6
6
6
5
5
5
2
6
6
6
5
5
5
C
C
H
H
CH(OH)CH
CH CH OH
2
CH
3
5
C
C
H
H
COCH CH
CH CHO
2
3
2
2
2
C H COCH(OH)C H
6
C H COCOC H
6
5
6
6
5
5
CH ;; CCH
CH (CH
C H OH
OH
CH OH
CH ;; CCH
CH (CH
C H OH
OH
2
2
3
2
)
6
2
3
2
)
6
CH
2
OH
6
11
6 11
a
Products were characterized by comparison of their physical and spectra data with
authentic samples.
b
Yields refer to isolated products.

ORDER
REPRINTS
1
176
Tajbakhsh, Lakouraj, and Fadavi
As shown in Eq. (1), when an equimolar amount of benzhydrol and cyclohex-
anol was treated with one molar ratio of reagent only benzylic alcohol was
selectively oxidized and cyclohexanol remained unchanged.
In the oxidation of alcohols the overoxidation of products to the corre-
sponding carboxylic acids was not at all observed.
In addition, we also report oxidative deprotection of benzylic trimethylsi-
lyl and THP ethers with this reagent under mild conditions (Sch. 1).
Similar to oxidation of alcohols benzylic trimethylsilyl and THP ethers
are efficiently converted to the corresponding carbonyl compounds using
ATPPD in refluxing acetonitrile using 1.15 : 1 molar ratio of oxidant to sub-
strate. The yields are high to excellent (Tables 2 and 3 entries 1–11). Under
the reaction condition allylic trimethylsilyl and THP ethers have been selec-
tively oxidized to their a,b-unsaturated carbonyl compounds without any
cleavage of the carbon–carbon double bonds (Tables 2 and 3 entry 12).
a-Hydroxy trimethylsilyl and THP ethers, have been converted to their
a-diketone in high yield (Tables 2 and 3 entry 15).
ATPPD cannot oxidize aliphatic trimethylsilyl and THP ethers. This che-
moselectivity was examined by the following competitive reactions [Eqs. (2)
and (3)].
ATPPD
o-CH OC H CH OSiMe þ n-Octan-OSiMe ƒƒƒ!
3
6
4
2
3
3
o-CH3OC6H4CHO þ n-Octan-OSiMe3
ð2Þ
ð3Þ
ðunchangedÞ
ATPPD
p-ClC6H4CH2OTHP þ HC ;; CCH2OTHP ƒƒƒ!
p-ClC H CHO þ HC ;; CCH OTHP
6
4
2
ðunchangedÞ
As shown in above equations, when an equimolar amount of benzylic tri-
methylsilyl or THP ethers and aliphatic trimethylsilyl or THP ethers were trea-
ted with one molar ratio of reagent, only benzylic trimethylsilyl or THP ethers
were selectively oxidized.
In conclusion, we report that ATPPD is easily prepared as a stable powder
which can be kept for months without loosing its activity. In all reactions
1
–1.15 equivalents of the oxidant were consumed which shows the efficiency
of the reagent and advantage of this oxidant in comparison with some other
peroxodisulfate derivatives. Mildness of reaction conditions, short reaction
ATPPD
R R CHOX ƒƒƒƒƒƒƒƒƒ! R R CO
Scheme 1.
1
2
1
2
CH3CN=Reflux
X¼H; SiMe3;THP

ORDER
REPRINTS
Oxidation of Alcohols and Silyl and THP-Ethers with ATPPD
1177
CN.
Table 2. Oxidation of trimethylsilyl ethers with ATPPD in refluxing CH
3
b
Time Yield
(%)
a
Entry
Substrate
Product
(min)
1
2
3
4
5
6
7
8
9
C
p-ClC
6
H
5
CH
2
OSiMe
CH OSiMe
3
C
6
H
5
CHO
p-ClC CHO
o-ClC H CHO
15
20
20
15
15
15
15
20
25
20
30
25
30
35
30
60
60
60
95
93
94
96
98
97
95
92
86
88
83
84
82
85
85
—
—
—
6
H
4
2
3
6 4
H
o-ClC H CH OSiMe
6
4
2
3
6 4
p-CH
o-CH
3
C
C
6
H
H
4
CH
2
2
OSiMe
OSiMe
3
3
p-CH
o-CH
3
C
C
6
H
H
4
CHO
CHO
3
6
4
CH
3
6
4
p-CH OC H CH OSiMe
3
p-CH OC H CHO
3 6 4
6
4
2
3
3
o-CH OC H CH OSiMe
2
o-CH OC H CHO
3 6 4
3
6
4
(C
6
H
5
)
2
CHOSiMe
CH(OSiMe
3
(C
p-ClC
C H COCH
3
6
H
5
)
2
CHO
p-ClC
6
H
4
3
)C
6
H
5
6
H
COC H
4 6 5
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
C H CH(OSiMe )CH
6
5
3
3
6
5
p-ClC
C
6
H
4
CH(OSiMe
CH 55 CHCH OSiMe
3
)CH
3
3
p-ClC
C H CH 55 CHCHO
6 4 3
H COCH
6
H
5
2
3
6 5
C H CH(OSiMe )CH CH
C H COCH CH
6
6
6
5
5
5
3
2
6
6
6
5
5
5
2
3
C
C
H
H
CH
COCH(OsiMe
2
CH
2
OSiMe
3
C
C
H
H
CH
2
CHO
3
)C
6
H
5
6
COCOC H
5
CH ;; CCH OSiMe
CH ;; CCH OSiMe
CH
2
3
2
3
CH
3
(CH
2
)
6
CH
2
OSiMe
3
3
(CH
2 6 2
) CH OSiMe
C
6
H
11OSiMe
3
C
6
H11OSiMe
3
a
Products were characterized by comparison of their physical and spectra data with
authentic samples.
b
Yields refer to isolated products.
time, ease of work-up procedure, stability of the reagent, and high yield of pro-
ducts are among the other advantages of this method which make ATPPD a
benchtop and versatile reagent for the oxidation of alcohols, trimethylsilyl
and THP ethers to the corresponding carbonyl compounds.
EXPERIMENTAL
1
IR spectra were determined on a shimadazu model 8300. H NMR spectra
were recorded with a bruker advance DPX 250 MHz spectrometer. Solvent
was freshly distilled. Trimethylsilyl ethers and THP ethers were prepared
[27,28]
according to the literature procedure.
Preparation of Allyltriphenylphosphonium Peroxodisulphate
[26]
To an aqueous solution of allyltriphenylphosphonium bromide (24 g,
.062 mol; in 100 mL of mild hot water) was added a solution of potassium
0

ORDER
REPRINTS
1
178
Tajbakhsh, Lakouraj, and Fadavi
Table 3. Oxidation of THP ethers with ATPPS in refluxing CH CN.
3
b
Time
(min)
Yield
(%)
a
Entry
Substrate
OTHP
CH OTHP
Product
1
2
3
4
5
6
7
8
9
C
6
H
5
CH
2
C
6
H
5
CHO
p-ClC CHO
o-ClC H CHO
20
20
20
15
15
15
20
20
25
20
25
35
30
60
40
60
60
60
96
90
91
93
94
97
96
90
86
87
85
83
80
40
80
—
—
—
p-ClC
6
H
4
2
6 4
H
o-ClC H CH OTHP
6
4
2
6 4
p-CH
o-CH
3
C
C
6
H
H
4
CH
CH
2
OTHP
OTHP
p-CH
o-CH
3
C
C
6
H
H
4
CHO
CHO
3
6
4
2
3
6
4
p-CH OC H CH OTHP
3
p-CH OC H CHO
3 6 4
6
4
2
o-CH OC H CH OTHP
2
o-CH OC H CHO
6
3
6
4
3
4
(C
p-ClC
C H CH(OTHP)CH
6
H
5
)
2
CHOTHP
(C
p-ClC
C H COCH
3
6
H
5
)
2
CO
6
H
4
CH(OTHP)C
6
H
5
6 4 6 5
H COC H
10
11
12
13
14
15
16
17
18
6
5
3
6
5
p-ClC
6
H
4
CH(OTHP)CH
3
3
5
6 4 3
p-ClC H COCH
C H CH 55 CHCHO
C
6
H
5
CH 55 CHCH
2
OTHP
6 5
C H CH(OTHP)CH CH
C H COCH CH
6
6
6
5
5
5
2
6
6
6
5
5
5
2
3
5
C
C
H
H
CH
2
CH
2
OTHP
COCH(OTHP)C
C
C
H
H
CH
2
CHO
6
H
6
COCOC H
CH ;; CCH OTHP
CH ;; CCHO
CH (CH CHO
Cyclohexanon
2
CH
3
(CH
2
)
6
CH
2
OTHP
3
2 6
)
C H11OTHP
6
a
Products were characterized by comparison of their physical and spectra data with
authentic samples.
b
Yields refer to isolated products.
peroxodisulfate (8.38 g, 0.031 mol; in 170 mL of H O) and the mixture was
2
stirred at room temperature for 3 hr. The resulting white solid product was
filtered, washed with distilled water (50 mL) and dried in a desiccator under
vaccum over phosphorus pentoxide to give product.(23 gr., 92%). M.p.
150–1528C
water
ðCH 55 CHCH ðPhÞ PÞ Br þ K S O ƒƒƒ!
þ
ꢀ
2
2
2
3
2
2
8
rt=3 hr
ðCH2 55 CHCH2ðPhÞ PÞ S2O þ 2 KBr
3
2
8
1
H NMR (250 MHz) d ¼ 7.85(m, 15H, (C H ) P), 5.72–5.75 (m, 1H,
6
5 3
CH 55 CH–), 5.35–5.41 (m, 2H, CH 55 CH–), 4.56–4.65 (m, 2H, –CH –
2
2
2
P(Ph)3); IR (KBr) 3010, 2900, 1400, 1300, and 1100 (–O–SO –O–),
2
1000, 925, 850, 710, 675. Found: C, 63%; H, 4.9%; S, 7.9% Calc for
C H P S O : C, 63.14%; H, 5.04%; S, 8.02%.
4
2 40 2 2 8

ORDER
REPRINTS
Oxidation of Alcohols and Silyl and THP-Ethers with ATPPD
1179
General Procedure for Oxidation of Alcohols, THP and
Silyl Ethers
Substrate (1 mmol) was dissolved in acetonitrile (10 mL) and oxidant
1.15 mmol) was added to it. The mixture was refluxed for specified time
Tables 1–3), until entire substrate was disappeared. The progress of reaction
(
(
was monitored by TLC (eluent: carbon tetrachloride/ethyl acetate 20 : 4 for
alcohols and 20 : 1 for trimethylsilylether and THP ethers). The reaction mix-
ture was allowed to cool to room temperature and filtered. The solid material
was washed with acetonitrile (20 mL) and combined filtrates were evaporated
on a rotary evaporator.
The crude material was purified on a silica gel plate to afford pure carbo-
nyl compound. Products were separated and were identified by the comparison
of their m.p., IR, NMR spectra, and b.p., with those reported for the authentic
samples.
ACKNOWLEDGMENT
We are thankful to the Mazandaran University for the partial support of
this work.
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2
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ORDER
REPRINTS
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Received in the USA April 22, 2003

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