Preparation and reactivity of polystyrene-supported iodosylbenzene sulfate: An efficient recyclable oxidizing system

Article abstract of DOI:10.1055/s-0030-1259011

A new polymer-supported hypervalent iodine reagent, polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate under solvent-free conditions. This new recyclable reagent effects clean and efficient oxidation of a wide range of alcohols and sulfides to the corresponding carbonyl compounds or sulfoxides in high conversions under mild conditions. The final products are conveniently separated from the polymeric byproduct by simple filtration and isolated in good purity after evaporation of solvent. Recycling of the resin is possible with minimal loss of activity after several reoxidations.

Full text of DOI:10.1055/s-0030-1259011

LETTER
2771
Preparation and Reactivity of Polystyrene-Supported Iodosylbenzene Sulfate:
An Efficient Recyclable Oxidizing System
ulfate -Min Chen,*a,b Xiao-Mei Zeng, Viktor V. Zhdankin*b
b
P
J
olystyren
i
e-Supp
a
orted
I
odos
n
ylbenzene
S
g
a
College of Biological and Chemical Engineering, Jiaxing University, 56 South Yuexiu Rd, Jiaxing 314001, P. R. of China
E-mail: chemcjm@yahoo.com.cn
b
Department of Chemistry and Biochemistry, University of Minnesota Duluth, 1039 University Dr., Duluth, MN 55812, USA
Fax +1(218)7267394; E-mail: vzhdanki@d.umn.edu
Received 14 September 2010
3
PhI(OAc)2 + 2 NaHSO4⋅H2O
(PhIO)3SO3 + 6 HOAc + Na2SO4
Abstract: A new polymer-supported hypervalent iodine reagent,
polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be
conveniently prepared by the reaction of polystyrene-supported (di-
acetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate
under solvent-free conditions. This new recyclable reagent effects
clean and efficient oxidation of a wide range of alcohols and sul-
1
Equation 1 Preparation of oligomeric iodosylbenzene sulfate (1)
Oligomeric iodosylbenzene sulfate (1) has been demon-
fides to the corresponding carbonyl compounds or sulfoxides in strated to be a highly reactive oxidant towards organic sul-
high conversions under mild conditions. The final products are con- fides, alcohols, and alkenes with a reactivity pattern
4
veniently separated from the polymeric byproduct by simple filtra-
similar to activated iodosylbenzene complexes. Howev-
tion and isolated in good purity after evaporation of solvent.
er, compound 1 has a significant disadvantage as a reagent
Recycling of the resin is possible with minimal loss of activity after
since its reactions with organic substrates lead to iodoben-
several reoxidations.
zene as the byproduct, which is difficult to recover and re-
Key words: polymers, iodine, oxidation, iodosylbenzene(III) sul-
fate, recyclable reagent
use because of the high volatility and solubility in organic
solvents. A strategy that completely avoids generating
product containing the iodobenzene is the use of a poly-
mer-supported reagent. The advantages of polymer-sup-
In the past two decades, hypervalent iodine compounds
ported reactive species are now widely recognized by
have been widely used in organic synthesis for various
organic chemists, and increasing exploitation of these sys-
1
synthetically useful oxidative transformations. The ad-
tem is occurring both in academic and industrial laborato-
vantages of using trivalent iodine compounds are the sim-
ple experimental operation and the low toxicity of the
reagents. One of the most widely used reagents, iodosyl-
5
ries. However, most of the previously reported polymer-
supported reagents, like polymer-supported analogues of
6
IBX, require a multistep preparation, and the repeated
benzene (PhIO) , is particularly important as an oxygen-
n
use of these polymers leads to significant degradation.
transfer agent that has found widespread application in
catalytic oxygenation reactions after the discovery of its
supreme efficacy as a source of oxygen atoms for oxida-
tions catalyzed by cytochrome P-450 and by discrete tran-
Herein, we report a facile preparation of novel polymer-
supported reagent, polystyrene-supported iodosylbenzene
sulfate (PS-IBS, 3), which is a highly reactive oxidant to-
ward organic sulfides and alcohols, respectively, in the
presence of KBr as catalyst in aqueous acetonitrile.
7
2
sition-metal complexes. However, the practical use of
iodosylbenzene is hampered by its low stability and po-
tentially explosive properties upon moderate heating and PS-IBS (3) can be conveniently prepared by treatment of
insolubility in most solvents as a result of its polymeric polystyrene-supported (diacetoxyiodo)benzene (PS-DIB,
3
8
structure. Recently, we have reported the preparation, X- 2) with sodium bisulfate monohydrate under solvent-free
ray crystal structure, and oxidative properties of oligomer- conditions (Scheme 1).9
ic iodosylbenzene sulfate (PhIO) ·SO (1), which is readi-
3
3
In a typical procedure PS-DIB and sodium bisulfate mon-
ohydrate were grinded intensively in a mortar at room
temperature for 10 minutes. The resulting mixture was left
to stay at room temperature overnight, then washed subse-
quently with water, acetone, and diethyl ether, and dried
in vacuum to give a yellow powder. The obtained resin,
ly available, water-soluble, and stable iodosylbenzene
4
analogue. Compound 1 can be conveniently prepared in
high yield by a solvent-free reaction of (diacetoxy-
iodo)benzene with sodium bisulfate monohydrate
(
Equation 1) and isolated as a yellow crystalline product
after crystallization from water. Single-crystal X-ray anal-
ysis of product 1 revealed a complex structure of alternat-
NaHSO4⋅H2O
I(OAc)2
(
3 3
IO) SO
ing copolymer containing one –OSO – fragment per three
– AcOH
– Na2SO4
2
a,b
4
PhIO units in the polymeric chain.
PS-DIB (2)
PS-IBS (3)
Scheme 1 Preparation of polystyrene-supported iodosylbenzene
sulfate (3).
SYNLETT 2010, No. 18, pp 2771–2774
x
x
.x
x
.2
0
1
0
Advanced online publication: 22.10.2010
DOI: 10.1055/s-0030-1259011; Art ID: S06110ST
Georg Thieme Verlag Stuttgart · New York
©

2
772
J.-M. Chen et al.
LETTER
PS-IBS, was characterized by IR spectroscopy and ele- sured by GC-MS with a prior column calibration using au-
mental analysis. The content of sulfur (S: 2.18%) corre- thentic samples of reactants and products. The reaction
sponds to the loading of 0.68 mmol/g. Results of products were isolated by removal of the solid resin and
elemental analysis imply that PS-DIB (2) is converted al- aqueous workup of organic solution; products were iden-
most quantitatively into PS-IBS (3). PS-IBS is stable in air tified by direct comparison of the retention times and MS
1
and no decomposition has been observed over a period of data with those obtained for authentic samples or by H
one week at room temperature. For longer periods PS-IBS NMR. The results are summarized in Table 1. Under these
should be stored away from direct sunlight and in a refri- reaction conditions primary alcohols were selectively ox-
gerator.
idized to the corresponding aldehydes (entries 1–3) and
secondary alcohols to ketones (entries 4–7). Interestingly,
previously reported oxidations of primary alcohols using
PS-DIB (2) in the presence of KBr afforded carboxylic ac-
The oxidative properties of PS-IBS were evaluated by the
reaction with various alcohols 5 and sulfides 6
1
0
(
Scheme 2). Reactions were performed in aqueous ace-
1
1
ids or lactones. At the same time, however, the reaction
tonitrile in the presence of catalytic amount of KBr at
room temperature using excess of PS-IBS (3) (0.7 mol
equiv of reagent 3, which is approx. two iodosyl groups
per one molecule of a substrate). Conversions were mea-
of monomeric sulfate 1 with benzylic alcohols afforded
4a
exclusively aldehydes, which is in agreement with our
results (entries 1–3). Dialkyl, diaryl, and aryl alkyl sul-
Table 1 Oxidation of Organic Substrates Using PS-IBS (3)a
OH
R2
O
O
S
O O
S
PS-IBS (3)
R1
or
R1
R2
and
S
or
R1
R2
R1
R2
R1
R2
5
6
7
8
9
Entry
Substrate
5a
R1
R2
Product
7a
Time (h)
Conversion (%)b Yield (%)c
1
2
3
4
5
6
7
8
9
Ph
H
10
10
10
2
>99
>95
>99
>99
>99
>99
>99
>99
>99
>86
>99
>99
>99
>99
>99
>99
>99
>99
0
91
5b
5c
4-O NC H
H
7b
90
2
6
4
4
3-O NC H
H
7c
98
2
6
5d
5e
Ph
Ph
Me
Et
7d
95
7e
3
92
5f
-(CH ) -
7f
3
60
2
5
5g
Bn
Me
7g
12
1
75
6a
n-Bu
n-Bu
8a
89
6b
6c
-(CH ) -
8b
2
60
2
5
1
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
9
0
Ph
Me
Me
Me
Me
Et
8c
14
2
72
6d
6e
4-MeOC H
8d
92
6
4
4-O NC H
4
8e
2.5
2
90
2
6
6f
4-ClC H
8f
88
6
4
6g
Ph
Ph
Ph
8g
10
2
78
6h
6i
Bn
Ph
8h
93
8i
3
99
6j
4-CNC H
Me
Me
CF3
–
8j+9j
8k+9k
–d
12
24
48
1
8j/9j = 1:10
6
4
6k
6l
4-CHOC H
8k/9k = 3:1
6
4
4-BrC H
–
6
4
2
Ph3P
–
Ph P=O
>99
99
3
a
All oxidations were carried out with 0.7 equiv of PS-IBS (3) and KBr (10 mol%) in MeCN–H O (5:1) at r.t. All products were isolated and
2
identified by comparison of their MS and NMR spectra with commercially available samples.
b
GC data.
Isolated yields.
No reaction observed even at reflux condition for 48 h.
c
d
Synlett 2010, No. 18, 2771–2774 © Thieme Stuttgart · New York

LETTER
Polystyrene-Supported Iodosylbenzene Sulfate
2773
fides were oxidized predominantly to sulfoxides (entries Acknowledgment
8
–16). However, the oxidation of aryl alkyl sulfides 6j
Jiang-Min Chen thanks the financial Foundation of Jiaxing Univer-
sity for supporting his visit to University of Minnesota Duluth. This
work was supported by a research grant from the National Science
and 6k bearing the electron-withdrawing aldehyde or ni-
trile groups required generally longer reaction time and
afforded mixtures of sulfoxides and sulfones (entries 17 Foundation (CHE-1009038).
and 18). Furthermore, the sulfide 6l with a strong elec-
tron-withdrawing CF group could not be oxidized using
PS-IBS/KBr system even after 48 hours of reflux (entry
3
References and Notes
1
9).
(1) For books and selected reviews on hypervalent iodine
chemistry, see: (a) Varvoglis, A. Hypervalent Iodine in
Organic Synthesis; Academic Press: London, 1997.
The PS-IBS/KBr system can also be used for the oxida-
tion at phosphorus atom, as illustrated by the oxidation of
triphenylphosphine to triphenylphosphine oxide in quan-
titative yield (entry 20). The final products of all oxida-
tions can be conveniently separated from byproduct by
simple filtration and isolated in good purity after evapora-
tion of solvent.
(
b) Hypervalent Iodine Chemistry; Wirth, T., Ed.; Springer:
Berlin, 2003. (c) Koser, G. F. Aldrichimica Acta 2001, 34,
89. (d) Koser, G. F. Adv. Heterocycl. Chem. 2004, 86, 225.
(
(
e) Moriarty, R. M. J. Org. Chem. 2005, 70, 2893.
f) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108,
5
(
299. (g) Ladziata, U.; Zhdankin, V. V. ARKIVOC 2006,
ix), 26. (h) Ciufolini, M. A.; Braun, N. A.; Canesi, S.;
Ousmer, M.; Chang, J.; Chai, D. Synthesis 2007, 3759.
i) Koser, G. F. Adv. Heterocycl. Chem. 2004, 86, 225.
Considering current research activity toward the develop-
ment of catalytic systems based on hypervalent iodine
chemistry,
tions (Scheme 2) using catalytic amount of PS-IB (4).
However, all our attempts to generate PS-IBS (3) from
resin 4 in solution were unsuccessful and thus the catalytic
version of these oxidations does not seem to be possible.
(
1
m–s
(j) Zhdankin, V. V. Science of Synthesis, Vol. 31a; Thieme:
Stuttgart, 2007, Chap. 31.4.1, 161. (k) Ladziata, U.;
Zhdankin, V. V. Synlett 2007, 527. (l) Quideau, S.;
Pouysegu, L.; Deffieux, D. Synlett 2008, 467. (m) Dohi, T.;
Kita, Y. Chem. Commun. 2009, 2073. (n) Ochiai, M.;
Miyamoto, K. Eur. J. Org. Chem. 2008, 4229.
it would be interesting to test these oxida-
(o) Yusubov, M. S.; Zhdankin, V. V. Mendeleev Commun.
2
010, 20, 185. (p) Zhdankin, V. V. ARKIVOC 2009, (i), 1.
NaHSO4⋅H2O
(
(
q) Uyanik, M.; Ishihara, K. Chem. Commun. 2009, 2086.
r) Ngatimin, M.; Lupton, D. W. Aust. J. Chem. 2010, 63,
I(OAc)2
AcOOH,
AcOH
6
53. (s) Yusubov, M. S.; Nemykin, V. N.; Zhdankin, V. V.
PS-DIB (2)
Na2SO4,
AcOH
Tetrahedron 2010, 66, 5745.
(
2) (a) Groves, J. T.; Nemo, T. E.; Myers, R. S. J. Am. Chem.
Soc. 1979, 101, 1032. (b) Cytochrome P450: Structure,
Mechanism, and Biochemistry; Ortiz de Montellano, P. R.,
Ed.; Kluwer Academic/Plenum Publishers: New York,
(
IO)3SO3
I
2
005. (c) Metalloporphyrins in Catalytic Oxidations;
Sheldon, R. A., Ed.; Marcel Dekker: New York, 1994.
d) Rose, E.; Andrioletti, B.; Zrig, S.; Quelquejeu-Etheve,
PS-IB (4)
PS-IBS (3)
(
M. Chem. Soc. Rev. 2005, 34, 573. (e) Simonneaux, G.;
Tagliatesta, P. J. Porphyrins Phthalocyanines 2004, 8,
1166. (f) Bernadou, J.; Meunier, B. Adv. Synth. Catal. 2004,
3
46, 171. (g) Vinhado, F. S.; Martins, P. R.; Iamamoto, Y.
O
Curr. Top. Catal. 2002, 3, 199. (h) Meunier, B.; Robert, A.;
Pratviel, G.; Bernadou, J. Porphyrin Handbook 2000, 4,
119. (i) Groves, J. T.; Shalyaev, K.; Lee, J. Porphyrin
Handbook 2000, 4, 17. (j) Moro-oka, Y.; Akita, M. Catal.
Today 1998, 41, 327. (k) Noyori, R. Asymmetric Catalysis
in Organic Synthesis; Wiley: New York, 1994.
or
OH
R1
R2
or
S
7
R1
R2
R1
R2
O
O
O
5
6
S
and
S
R1
R2
R1
R2
8
9
(
3) Moriarty, R. M.; Kosmeder, J. W.; Zhdankin, V. V.
Iodosylbenzene, In Encyclopedia of Reagents for Organic
Synthesis; Wiley: Chichester, 2004.
4) (a) Koposov, A. Y.; Netzel, B. C.; Yusubov, M. S.;
Nemykin, V. N.; Nazarenko, A. Y.; Zhdankin, V. V. Eur.
J. Org. Chem. 2007, 4475. (b) Nemykin, V. N.; Koposov,
A. Y.; Netzel, B. C.; Yusubov, M. S.; Zhdankin, V. V. Inorg.
Chem. 2009, 48, 4908. (c) Yusubov, M. S.; Yusubova,
R. Y.; Funk, T. V.; Chi, K.-W.; Zhdankin, V. V. Synthesis
Scheme 2 Oxidation of alcohols 5 and sulfides 6 using PS-IBS (3)
as a recyclable reagent
(
In conclusion, we have prepared a novel polymer-support-
ed iodosylbenzene sulfate (PS-IBS, 3), which can find
practical application as a readily available, stable, and re-
cyclable reagent with a reactivity pattern similar to that of
its monomeric analogue, iodosylbenzene sulfate 1. Treat-
ing alcohols with PS-IBS in the presence of catalytic
amount of KBr allowed in most cases complete conver-
sion into aldehydes or ketones, while treating sulfides led
to sulfoxides or sulfones, in excellent yields, under mild
conditions and with easy workup.
2
009, 2505. (d) Neu, H. M.; Yusubov, M. S.; Zhdankin,
V. V.; Nemykin, V. N. Adv. Synth. Catal. 2009, 351, 3168.
e) Geraskin, I. M.; Pavlova, O.; Neu, H. M.; Yusubov,
(
M. S.; Nemykin, V. N.; Zhdankin, V. V. Adv. Synth. Catal.
2009, 351, 733.
(
5) Togo, H.; Sakuratani, K. Synlett 2002, 1966.
Synlett 2010, No. 18, 2771–2774 © Thieme Stuttgart · New York

2
774
(
J.-M. Chen et al.
LETTER
6) (a) Mülbaier, M.; Giannis, A. Angew. Chem. Int. Ed. 2001,
0, 4393. (b) Sorg, G.; Mengel, A.; Jung, G.; Rademann, J.
3.0 mmol) were grinded intensively in a mortar at r.t. for 10
min. The resulting mixture was left to stay at r.t. overnight,
4
Angew. Chem. Int. Ed. 2001, 40, 4395. (c) Lei, Z. Q.; Ma,
H. C.; Zhang, Z.; Yang, Y. X. React. Funct. Polym. 2006, 66,
then washed with H O (3 × 3 mL), acetone (3 × 3 mL), and
2
give a yellow powder (1.45 g). Elemental analysis: S, 2.18%
2
Et O (3 × 3 mL) subsequently, and then dried in vacuum to
840. (d) Chung, W.-J.; Kim, D.-K.; Lee, Y.-S. Tetrahedron
Lett. 2003, 44, 9251. (e) Kim, D.-K.; Chung, W.-J.; Lee,
Y.-S. Synlett 2005, 279. (f) Ladziata, U.; Willging, J.;
Zhdankin, V. V. Org. Lett. 2006, 8, 167. (g) Karimov,
R. R.; Kazhkenov, Z.-G. M.; Modjewski, M. J.; Peterson,
E. M.; Zhdankin, V. V. J. Org. Chem. 2007, 72, 8149.
7) Structure 3 is assigned for polystyrene-supported iodosyl-
benzene sulfate based on X-ray single crystal data for the
monomeric analogue 1, which has been prepared using a
similar solid-state procedure. We realize that the presence of
the polystyrene chain may have a significant effect on the
actual structure of the iodosylbenzene sulfate moiety. The
ESI-MS study of compound 1 in aq solution indicates the
(loading of S: 0.68 mmol/g). IR (KBr): n = 3406, 2923,
–
1
1628, 1481, 1406, 1118, 1004, 819, 766, 619 cm .
(10) General Procedure for Oxidations Using PS-IBS
To a solution of sulfide 6 (0.2 mmol) or alcohol 5 (0.2 mmol)
in aq MeCN (2 mL of MeCN–H O, 5:1) was added PS-IBS
2
(
3 (206 mg, 0.140 mmol) and KBr (2.4 mg, 0.02 mmol) at r.t.,
and the mixture was magnetically stirred until the sulfide or
alcohol was consumed (monitored by TLC). The mixture
was filtered, and the resin was washed with EtOAc (3 × 1
mL). The filtrate was washed with sat. NaHCO (3 mL) [for
3
alcohols, the filtrate may be washed with 5% H SO (3 mL)
2
4
before this operation], then extracted with EtOAc (3 × 2
mL). The combined organic solution was washed with brine
(3 mL), water (3 mL), and dried over Na SO . The solvent
+
presence of hydroxy(phenyl)iodonium ion, [PhI(OH)] and
4
a,b
hydrated iodosylbenzene, PhI(OH)2. It is possible that
similar polymer-bound iodine(III) moieties are present the
structure of resin 3.
2
4
was evaporated to yield respective products 7–9; the
products were identified by comparison of their MS and
NMR spectra with commercially available samples.
(11) (a) Tohma, H.; Maegawa, T.; Kita, Y. Synlett 2003, 723.
(b) Tohma, H.; Maegawa, T.; Takizawa, S.; Kita, Y. Adv.
Synth. Catal. 2002, 344, 328.
(
8) (a) Chen, J. M.; Huang, X. Synthesis 2004, 2459. (b) Togo,
H.; Nogami, G.; Yokoyama, M. Synlett 1998, 534.
(c) Togo, H.; Abe, S.; Nogami, G.; Yokoyama, M. Bull.
Chem. Soc. Jpn. 1999, 72, 2351.
9) Preparation of PS-IBS (3)
(
8
PS-DIB (2) (1.430 g, 3.0 mmol) and NaHSO ·H O (0.414 g,
4
2
Synlett 2010, No. 18, 2771–2774 © Thieme Stuttgart · New York

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