An efficient and green oxidation of vicinal diols to aldehydes using polymer-supported (diacetoxyiodo)benzene as the oxidant

Article abstract of DOI:10.1055/s-2007-970745

An operationally simple and clean oxidation of a variety of vicinal diols to aldehydes using polymer-supported (diacetoxyiodo)benzene (PSDIB) has been developed in high to excellent yields. Protecting groups such as OAc, OR, OBn, OBz and isopropylidene in the substrates were found to be stable under these reaction conditions. The regenerated PSDIB could be reused for the same reaction, affording oxidation products in high yield and purity. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-970745

LETTER
619
An Efficient and Green Oxidation of Vicinal Diols to Aldehydes Using
Polymer-Supported (Diacetoxyiodo)benzene as the Oxidant
Oxidation of
V
e
icinal
D
iol
n
s
U
sing
P
oly
-
mer-Sup
E
ported(Diaceto
r
xyiodo)benzen
C
e
hen,* Bin Xie, Ping Zhang, Jian-Feng Zhao, Hui Wang, Lei Zhao
Department of Chemistry, Fudan University, Shanghai 200433, P. R. of China
Fax +86(21)65643811; E-mail: rfchen@fudan.edu.cn
Received 18 September 2006
This paper is dedicated to Prof. Pei-Ling Xu on the occasion of her 80th birthday.
Polymer-supported hypervalent iodine reagents have been
used in a wild variety of oxidation and radical reactions in
organic synthesis due to their versatility, low toxicity and
high reactivity.16 The reaction products can be obtained by
Abstract: An operationally simple and clean oxidation of a variety
of vicinal diols to aldehydes using polymer-supported (diacetoxy-
iodo)benzene (PSDIB) has been developed in high to excellent
yields. Protecting groups such as OAc, OR, OBn, OBz and iso-
propylidene in the substrates were found to be stable under these re- simple filtration to remove the polymer-supported
action conditions. The regenerated PSDIB could be reused for the
reagent, and regeneration and reuse of the recovered poly-
same reaction, affording oxidation products in high yield and purity.
mer-supported reagents are possible, thus providing an
Key words: polymer-supported (diacetoxyiodo)benzene, vicinal
diols, oxidative cleavage, aldehydes
environmentally benign system. However, to the best of
our knowledge there has been no report so far describing
the use of polymer-supported hypervalent iodine reagents
to oxidize vicinal diols into the aldehydes. Herein, we
It is well known that oxidative cleavage of vicinal diols report the successful development of an efficient, simple
using periodic acid1 and lead tetraacetate2 are the most and synthetically useful procedure for the highly selective
classical methods for the preparation of aldehydes in oxidative cleavage of vicinal diols to aldehydes using
organic synthesis. The use of these two highly selective polymer-supported (diacetoxyiodo)benzene (PSDIB).
oxidants is strongly restricted by periodic acid’s insolubil-
ity in organic solvents, and lead tetraacetate is difficult to
store and handle for large scale utilization in industry.
O
O
Several oxidants, such as ceric ammonium nitrate,3 Ph3Bi/
NBS/K2CO3,4 CrO3,5 NIS,6 thallium nitrate,7 xenic acid,8
ammonium chlorochromate (ACC),9 pyridinium chloro-
BnO
O
OH
OH
OAc
OAc
11
chromate (PCC),10 and MnO2 have been reported to
1a
I
AcOH
serve this purpose, but many of these methods still suffer
from some drawbacks, including the need to employ a
stoichiometric amount of reagents, long reaction time,
producing a large amount of waste, and give unsatisfacto-
ry yields. Recently, an improved procedure using silica
gel supported sodium metaperiodate for oxidative cleav-
age of vicinal glycols12 was reported. However, the use of
excess NaIO4 makes this procedure impractical for indus-
trial application. In addition, there are two reports wherein
various vicinal diols were cleaved into the corresponding
aldehydes with O2-catalyzed iron–porphyrin complex13
and Ru(PPh3)3Cl/C,14 but the low chemoselectivity of
these two oxidation systems rendered them defective. (Di-
acetoxyiodo)benzene was also used for oxidative cleav-
age of glycols forming carbonyl compounds,15 though
suffering the difficulty of removing the byproduct iodo-
benzene from the products. As a result, there is still room
for the development of efficient, highly selective and
environmentally benign methods for this transformation
under mild reaction conditions from both industrial and
green chemistry perspectives.
O
O
AcOOH
I
BnO
CHO
O
2a
Scheme 1 Oxidative cleavage of 1a, regeneration and recycling of
used PSDIB
The PSDIB-mediated oxidative cleavage of benzyl 2,3-O-
isopropylidene-a-D-mannofuranoside (1a) was initially
chosen as a representative vicinal diol for the discovery of
the appropriate conditions (Scheme 1). The loading of
PSDIB was 1.98 mmol/g as determined by elemental
analysis. We were pleased to observe that when a mixture
of 1a and 1.2 equivalents of PSDIB in CH2Cl2 was stirred
at room temperature for seven hours, the oxidation took
place smoothly and the corresponding aldehyde was
successfully isolated in 90% yield (Table 1). The choice
of solvents in this oxidation was crucial for the success.
Acetonitrile was good for the reaction (Table 1, entry 2).
The yield of 2a dropped dramatically in the case of
CH2Cl2–toluene mixture and reaction did not proceed at
all in the toluene, THF, dioxane, acetone, or DMF.
SYNLETT 2007, No. 4, pp 0619–0622
0
1.
0
3.
2
0
0
7
Advanced online publication: 21.02.2007
DOI: 10.1055/s-2007-970745; Art ID: W19206ST
© Georg Thieme Verlag Stuttgart · New York

620
F.-E. Chen et al.
LETTER
The recovered polymer was re-oxidized with peracetic
acid following literature precedent17 and the oxidations
were repeated without loss of activity.
Table 1 Oxidation of Vicinal Diol 1a with PSDIB in Different
Solventsa
Entry
Solvent
Time (h)
Yield (%)b
With these observations in hand, we decided to broaden
its field of application by looking at the scope and limita-
tion of this oxidation. As depicted in Table 2, all the tested
substrates were smoothly oxidized into the corresponding
aldehydes in excellent yields (entries 1–13). This proce-
dure is highly chemoselective allowing oxidation of
vicinal diols without affecting such functionalities as OBn
(entries 1, 13), OBz (entry 2), OAc (entry 4), OR (entries
3, 9, 11), OH (entry 5), isopropylidene (entries 1–8).
1
2
3
4
5
6
7
8
CH2Cl2
7
8.5
13
50
50
50
45
50
90
80
43
nrc
2
MeCN
CH2Cl2–toluene (1:1)
toluene
THF
acetone
nr
nr
nr
In conclusion, we have developed a simple and environ-
mentally benign protocol for the chemoselective oxida-
tion of a range of vicinal diols into the corresponding
aldehydes with high yields.29,30 Moreover, the PSDIB
consumed in this reaction can be regenerated efficiently
and repeatedly used for the same reactions with no loss of
activity. This procedure is characterized by mild condi-
tions, non-toxic byproducts and easy reaction work-up,
making it ideal for both laboratory and large-scale prepa-
rations.
DMF
dioxane
a All reactions were carried out according to typical procedure.
b Yield of isolated and fully characterized products.
c nr = no reaction.
Next, regeneration and recycling of the used PSDIB was
investigated based on this oxidation reaction. After the
first run, the polymer was recovered in almost quantitative
yield by simple filtration, washed with diethyl ether.
Table 2 Oxidation of Vicinal Diols with PSDIBa
OAc
I
(1.2 equiv)
R
OAc
R
CHO
OH
CH2Cl2, r.t.
OH
1
2
Entry
1
Vicinal diols
Time (h)
Products
Yield (%)b
O
O
O
O
O
O
O
O
O
O
O
O
O
7
9018
BnO
CHO
CHO
CHO
CHO
BnO
OH
OH
OH
OH
O
O
O
O
O
OH
OH
OH
OH
2a
1a
O
O
O
2
3
4
6.5
9019
8520
8421
BzO
BzO
O
O
O
2b
1b
7
EtO
EtO
2c
1c
7
AcO
AcO
2d
1d
Synlett 2007, No. 4, 619–622 © Thieme Stuttgart · New York

LETTER
Oxidation of Vicinal Diols Using Polymer-Supported (Diacetoxyiodo)benzene
621
Table 2 Oxidation of Vicinal Diols with PSDIBa (continued)
OAc
I
(1.2 equiv)
R
OAc
R
CHO
OH
CH2Cl2, r.t.
OH
1
2
Entry
5
Vicinal diols
Time (h)
Products
Yield (%)b
O
O
O
O
7
8222
HO
1e
O
OH
HO
CHO
O
O
OH
2e
O
O
O
6
7
7
7
8623
OH
CHO
O
O
OH
O
2f
1f
O
O
O
9824
Et
CHO
Et
1g
O
OH
O
O
OH
2g
OH
O
O
O
8
9
7
7
9513
O
CHO
O
OH
2h
1h
CHO
OMe
OH
9125
MeO
OH
2i
MeO
1i
O
CHO
OH
O
OH
10
11
12
6
8
7
9026
8727
9225
Cl
2j
Cl
1j
OH
OH
CHO
OHC
2k
1k
OH
CHO
OH
MeO
MeO
2l
1l
OH
BnO
CHO
BnO
13
7
9228
2m
OBn
OH
1m
a All reactions were performed according to the typical procedure.
b Yield of isolated and fully characterized products.
Synlett 2007, No. 4, 619–622 © Thieme Stuttgart · New York

622
F.-E. Chen et al.
LETTER
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(29) Preparation of the Polymer-Supported (Diacetoxy-
iodo)benzene (PSDIB).
To a mixture of CCl4 (20 mL), H2SO4 (50%, 20 mL) and
nitrobenzene (100 mL) was added polystyrene (5.0 g), I2
(5.0 g, 19.7 mmol) and I2O5 (4.0 g, 12 mmol) at r.t. The
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iodinated polystyrene (6.2 g). To Ac2O (145 mL, 1.54 mol)
was added dropwise 30% H2O2 (40 mL, 0.35 mol) and the
solution was stirred at 40 °C for 4 h. Then iodinated
polystyrene (6.2 g) was added and stirring was continued
overnight at the same temperature. After cooling the mixture
to r.t., Et2O (100 mL) was added into the mixture. The
precipitates were collected by filtration, washed with Et2O
(2 × 20 mL) and dried in vacuo to give PSDIB (6.5 g). The
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(30) Oxidation of 1a.
To a solution of 1a (3.1 g, 10 mmol) in CH2Cl2 (40 mL) was
added PSDIB (6.06 g, 12 mmol). Then, the reaction mixture
was stirred at r.t. for 7 h. Thereafter, the polymer was filtered
and washed with CH2Cl2 (3 × 8 mL). The filtrate was poured
into H2O (45 mL), and extracted with CH2Cl2 (3 × 10 mL).
The combined organic layer was washed with H2O (3 × 10
mL), dried over Na2SO4, filtered, and the solvent was
evaporated in vacuo to give crude product, which was
recrystallized from PE (60–90) to afford pure 2a (2.5 g,
90%) as a white powder; mp 81.5–83 °C; [a]D25 +28.2 (c 1.0,
acetone). IR (KBr): n = 2935, 1750, 1361, 749 cm–1. 1H
NMR (400 MHz, CDCl3): d = 1.26, 1.40 (s, each 3 H, i-Pr),
4.42 (d, 1 H, J = 4 Hz, C3-H), 4.49 (d, J = 1 H, 12 Hz, C2-H),
4.67 (t, 2 H, J = 5.6 Hz, CH2C6H5), 5.07 (dd, 1 H, J = 4.8, 5.6
Hz, C4-H), 5.27 (s, 1 H, C1-H), 7.26–7.35 (m, 5 H, ArH),
9.65 (s, 1 H, CHO). GCMS: m/z (%) = 263 [M – CH3]+, 187,
129, 113, 91 (100).
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Synlett 2007, No. 4, 619–622 © Thieme Stuttgart · New York