Facile and Clean Oxidation of Alcohols in Water Using Hypervalent Iodine (III) Reagents

Article abstract of DOI:10.1002/1615-4169(200206)344:3/4<328::AID-ADSC328>3.0.CO;2-S

The facile and efficient oxidation of various alcohols such as benzylic alcohols, primary alcohols, secondary alcohols, and diols in water using the hypervalent iodine(III) reagent, iodosobenzene (PhI=O), with KBr is described. Electrospray ionization (ESI) mass spectrometric studies on the behavior of PhI=O-KBr in aqueous solution suggested that these reactions are induced by the formation of highly reactive iodine species [PhI(Br)_nO^-]. Further development to recyclable polymer-supported iodine(III) reagent extends the utility of this reaction to afford an environmentally benign method.

Full text of DOI:10.1002/1615-4169(200206)344:3/4<328::AID-ADSC328>3.0.CO;2-S

FULL PAPERS
Facile and Clean Oxidation of Alcohols in Water Using
Hypervalent Iodine(III) Reagents
Hirofumi Tohma, Tomohiro Maegawa, Shinobu Takizawa, Yasuyuki Kita*
Graduate School of Pharmaceutical Sciences, Osaka University, 565-0871, Japan
Fax: ( ‡ 81)-6-6879-8229, e-mail: kita@phs.osaka-u.ac.jp
Received: October 31, 2001; Accepted: December 28, 2001
±
Abstract: The facile and efficient oxidation of various reactive iodine species [PhI(Br) O ]. Further devel-
n
alcohols such as benzylic alcohols, primary alcohols, opment to recyclable polymer-supported iodine(III)
secondary alcohols, and diols in water using the reagent extends the utility of this reaction to afford an
hypervalent iodine(III) reagent, iodosobenzene environmentally benign method.
(
PhIˆO), with KBr is described. Electrospray ioniza-
tion (ESI) mass spectrometric studies on the behavior
of PhIˆO-KBr in aqueous solution suggested that Keywords: alcohols; hypervalent compounds; iodine;
these reactions are induced by the formation of highly oxidation; water as solvent
Introduction
induced oxidation of various alcohols such as benzylic
alcohols, primary alcohols, secondary alcohols, and diols
Oxidation of alcohols to carbonyl compounds is a catalyzed by bromide salt in water, and a mechanistic
pivotal reaction in organic chemistry and numerous consideration of reactive iodine species from the basis of
methods using a variety of reagents and conditions have ESI mass spectrometry (MS).
been developed. Recent demands for eco-conscious
chemical processes have encouraged the development
[
1]
of several clean and practical oxidation reactions, and
promote further development of high-yielding, clean,
mild, safe, and economical methods for the oxidation of
Results and Discussion
alcohols. Hypervalent iodine reagents have been used Oxidation of Benzylic, Primary and Secondary
extensively in organic syntheses due to their low toxicity, Alcohols
[
2]
ready availability and easy handling. For example, the
highly utilized pentavalent iodine reagents such as Dess± In contrast to oxidations with iodo(V)-based reagents
[
3]
Martin periodinane (DMP) and o-iodoxybenzoic acid such as DMP and IBX, only a few examples of the
4]
(
IBX)[ mildly and efficiently oxidize alcohols to oxidation of alcohols using iodine(III) reagents have
[
7]
carbonyl compounds with high yields in organic solvents been described. Existing oxidation methods are lim-
such as CH Cl , DMSO, and acetone. However, despite ited to organic solvents and usually involve activation of
2
2
their utility, iodine(V) reagents are potentially explo- transition metal catalysts such as Ru, Yb, Co, and
[
7a, b,c]
sive, cannot be stored for a long time, and the iodine(III) Cr
or 2,2,6,6-tetramethyl-1-piperidinyloxy (TEM-
[
7d]
compounds (iodosobenzoic acid) generated after DMP PO) by an iodine(III) co-oxidant. As an exception,
or IBX)-induced oxidations are usually not utilized for readily oxidizable benzylic alcohol derivatives do not
oxidation reactions. Therefore, facile and efficient use of require catalysts, and can be oxidized using I(III)-
(
[
8a]
[
8b]
the readily available and relatively stable iodine(III) Al O under microwave irradiation.
2
3
reagents, in place of iodine(V) reagents, has been long
Various aqueous oxidation reactions have been de-
[
9]
desired. As part of our continued studies concerning the veloped since economic and environmental concerns
activation of trivalent iodine reagents using several encourage the use of water as a reaction medium.
[
5]
additives and solvents, we have briefly communicated Recently, we have achieved a novel catalytic activation
a mild and efficient oxidation of alcohols using iodoso- of PhIˆOusing a cationic surfactant, cetyltrimethylam-
benzene (PhIˆO) with an inexpensive inorganic salt, monium bromide (CTAB) under neutral conditions.[
KBr, in water under neutral conditions and its extension The low solubility of PhIˆOin water and in most
to an environmentally benign oxidation process using organic solvents normally limits the use of PhIˆO,
10]
[
6]
poly(diacetoxyiodo)styrene (PDAIS). In this paper, however, our micellar and reversed micellar systems
we present a full account of our studies on iodine(III)- have expanded the choice of solvents (from non-polar
328
¹ VCH Verlagsgesellschaft mbH, 69451 Weinheim, Germany, 1615-4150/02/3443+4-328 ± 337 $ 17.50-.50/0
Adv. Synth. Catal. 2002, 344, No. 3+4

Oxidation of Alcohols in Water Using Hypervalent Iodine(III) Reagents
FULL PAPERS
solvents to water) for hypervalent iodine oxidation.
When using 1.1 equiv. PhIˆOin the presence of
Thus, we first examined the oxidation of alcohol using 1.0 equiv. KBr, oxidation of primary alcohol 1k yielded
PhIˆO/CTAB in water. Oxidation of 2-octanol (1e) only carboxylic acid 2k (28 % yield of 2k and 68% of
catalyzed by CTAB (20 mol %) in water gave 2- recovered 1k for 5 h at r.t.) without yielding the
octanone (2e) in 67% yield. Thus, we re-investigated corresponding aldehyde.
the activation of PhIˆOin this reaction with a variety of
additives including alkali metal salts. As a result, the
addition of bromide ions such as NaBr, KBr, and LiBr Oxidation of Diols to Lactones
was found to remarkably activate PhIˆOto give 2e in
good yields [94% yield (KBr)], while salts other than During investigation of the above-mentioned reactions,
bromide (Na X: X ˆ F, Cl, I, HSO , BF , CO , ClO , we found that an oxidative condensation of primary al-
n
4
4
3
4
11]
[
OAc, NO ) did not catalyze the reaction effectively.
cohols mainly occurs as the water content decreases. For
3
We therefore chose KBr, the most economical alkali instance, oxidation of 1-pentanol (1k) using PhIˆO/KBr
metal bromide, for further studies. The oxidation of afforded pentyl pentanoate 3a in 77% yield along with
activated alcohols such as benzylic or allylic alcohols 23% yield of pentanoic acid 2k in the presence of water
proceeds in excellent yields simply by activating PhIˆO (10 equiv.). However, in the absence of water, the
with a small amount of water (10 equiv.), and without reaction rate slowed down due to the lowering of the
addition of KBr (entries 1 ± 3, Table 1). With benzyl efficiency of stirring. Thus, we subsequently applied this
alcohol (1c), the reaction rate is enhanced remarkably methodology to the oxidation of diols to lactones.
by adding a catalytic amount of KBr (entries 3 ± 4, Although many methods to prepare lactones by oxida-
Table 1). In contrast, a catalytic amount of KBr is tive condensation of diols have been performed using
indispensable for the oxidation of saturated primary and various stoichiometric oxidants, enzymes, and transition
secondary alcohols (Table 1). This PhIˆO/KBr system metal catalysts, most of them have been carried out in
is applicable to the oxidation of various primary and organic solvents or aqueous organic solvents. Further-
secondary alcohols in water to directly afford the more, the oxidations of diols, reported by Corey et
[
12a]
[12b]
[12c]
corresponding carboxylic acids and ketones in good al.,
Bueno et al.,
and Metz et al.
in DMSOor
yields. The results are listed in Table 1. CH Cl using I(V) reagents, such as IBX and DMP, yield
2
2
Table 1. Oxidation of alcohols 1 (for structures, see Figure 1) with PhIˆO/KBr in H O.
2
Entry
Substrate
Product
KBr [equiv.]
Time [h]
Yield [%][a]
quant.[
b]
1
2
3
4
5
6
7
8
9
1a
1b
1c
1c
1d
1e
1e
1e
2a
2b
2c
2c
2d
2e
2e
2e
none
none
none
0.2
1.0
none
0.2
30
6
24
2
[d, e]
78(94)
87[
e]
quant.
quant.[
trace
e]
4
48
24
8
4
3
24
7
4
48
5
12
3
[e]
94
98[
e]
1.0
1.0
1f
2f
quant.
quant.[
86
e]
e]
10
11
12
13
14
15
16
17
18
19
20
1g
1h
2g
2h
1.0
1.0
1.0
1.0
none
1.0
1.0
1.0
1.0
l-menthol 1i
3b-cholestanol 1j
l-menthone 2i
5a-cholestan-3-one 2j
quant.[
quant.
[
c]
1k
1k
1l
1m
1n
1o
1p
2k
2k
2l
2m
2n
2o
2p
±
83[
86[
c, e,f]
c, e,f]
c]
[
92
72[
c, f]
c, f]
c, f]
12
3
3
[
1.0
0.2
70
60[
[
[
[
[
[
[
a]
Yields are an average of two or more runs. Isolated yields unless otherwise noted.
b]
2
3
.5 equivalents of PhIˆOwere used.
c]
d]
e]
f]
.0 equivalents of PhIˆOwere used.
Yield in parenthesis is based on the consumed starting material.
Yields were determined by GC.
Small amount of ester was also obtained by oxidative condensation.
Adv. Synth. Catal. 2002, 344, 328 ± 337
329

FULL PAPERS
Yasuyuki Kita et al.
O
Ph
OH
1a
PhCO2H 2a
OH
O
O
OH
OH 1q
3b
2b
1b
O
OH
O
OH
O
2
c
1r
3c
3d
OH
1
c
O
PhCH(OH)Et 1d
PhCOEt 2d
OH
O
OH
O
1
e
2e
1s
4
4
OH
PhCOO
OH
PhCOO
O
O
3
e
2f
1f
2
2
O
OH
1
O 2g
OH OH
O
O
g
TsN
OH
1
TsN
O
2h
h
1
t
3f
L-menthol 1i
β-cholestanol 1j 5α-cholestan-3-one 2j
L-menthone 2i
O
O
3
HO
n
OH
CO2H
n
2
OH 1k
2
2k
2l
n=1 (1u)
n=2 (1v)
n=3 (1w)
n=1 (3g)
n=2 (3h)
n=3 (3i)
CO2H
CO2H
OH
OH
1l
O
O
OH
HO
1m
2m
1x
3j
OH 1n
3CO2H 2n
EtO2C
N3
4
EtO2C
N3
O5 H
4CO2H
2o
1o
Figure 1. Structures of alcohols 1 investigated and
the corresponding products 2 or 3.
2OH
2
CO H
2p
Ph
1p
Ph
the corresponding lactol derivatives. First, we examined Mechanistic Study: Detection of Reactive
the oxidation of cyclic diols in the presence of a small Intermediate in Water
amount of water (10 ± 20 equiv.). Consequently, oxida-
tion of various cyclic diols fixed by aromatic or aliphatic Regarding the behavior of iodine(III) reagents such as
rings gave the corresponding lactones in good yields [hydroxy(mesyloxy)iodo]benzene and [hydroxy(tosyl-
(
entries 2 ± 6, Table 2). On the other hand, oxidation of oxy)iodo]benzene in aqueous solution, Richter et al.
acyclic diols using PhIˆO/KBr exclusively yielded 5- demonstrated the presence of m-oxodiiodine(III) spe-
and 6-membered ring lactones (entries 9, 10, 12, Ta- cies on the basis of UV-Vis and NMR spectroscopic
ble 2). However, the yield of the 7-membered ring measurements along with potentiometric titration
[
14]
lactone 3i was 49% due to accompanying formation of 6- data. However, in our case, the addition of bromide
hydroxycaproic acid (33% yield) and adipic acid (18% salt complicated the mechanism. Thus, we considered
yield) under the reaction conditions (entry 11, Table 2). the following three reaction mechanisms: (1) in situ
Addition of KBr was indispensable for the oxidation of generation of I(V) species by disproportionation of
saturated diol 1u (entry 7, Table 2), while oxidative PhIˆOto PhIO and PhI in water, (2) in situ generation
2
lactonization of benzylic diol 1q proceeded slowly in the of bromine or bromonium ion by iodine(III)-induced
absence of KBr (entry 1, Table 2). This reaction also oxidation of bromide ion, and (3) the formation of
proceeded under diluted reaction conditions. However, activated I(III) species that contain I-Br bonding. To
an increase of the water content prolonged the reaction identify the nature of the reactive species, first, we
time.[
13]
examined the oxidation of 1e using PhIO /KBr, Br , and
2 2
NBS. Consequently, only a trace amount of 2e was
obtained when using PhIO /KBr even after 24 h. This
2
result meant that simple disproportionation of PhIˆO
does not occur. On the other hand, the reaction
proceeded slowly when using Br or NBS and afforded
2
2e in 30% or 64% yield after 24 h. However, in both
330
Adv. Synth. Catal. 2002, 344, 328 ± 337

Oxidation of Alcohols in Water Using Hypervalent Iodine(III) Reagents
FULL PAPERS
Table 2. Oxidation of diols 1q ± x (See Figure 1) with PhIˆO/KBr.
Entry
Substrate
Product
KBr [equiv.]
Time [h]
Yield [%][a]
1
2
3
4
5
6
7
8
9
1q
1q
1q
1r
1s
1t
1u
1u
1u
1v
1w
1x
3b
3b
3b
3c
none
0.2
1.0
1.0
0.2
1.0
none
0.2
1.0
1.0
24
5
2
3
2
7
24
8
3
4
54 (1q: 23)
89
91
quant.
3d ‡ 3e
79 (3d:3e ˆ 15:2)
92[
b]
3f
3g
3g
3g
3h
3i
±
quant.[
c]
[c]
quant.
89[
c]
1
1
1
0
1
2
49[
c]
1.0
1.0
6
6
87[
c]
3j
[
[
[
a]
Yields are an average of two or more runs. 2.5 equivalents of PhI ˆ Owere used. Isolated yields unless otherwise noted.
.0 equivalents of PhIˆOwere used.
Yields were determined by GC.
b]
3
c]
Figure 2. ESI-mass spectrum of reactive intermediates.
±
±
cases, brominated by-products were also obtained along (100 8C). Consequently, PhIO (Br) (4a), PhI(O ) Br
2
with the recovery of 1e. To clarify whether the actual (4b) and PhIOH(Br) (4c) were clearly detected by ESI
2
‡
reactive species are I-Br species or simple Br , next, we negative ion detection (Figure 2). To ensure the pres-
measured an ESI-mass spectrum of the aqueous solu- ence of these species, we then examined the behavior of
tion of PhIˆO/KBr in the absence of substrate. To 4-iodosylanisole in an analogous aqueous solution by
measure the ESI-mass spectrum at room temperature, ESI negative ion detection (Figure 3). As expected, the
±
which is the same temperature as the reaction con- analogous reactive species, (p-MeO)C H IO (Br), was
6
4
ditions, we adopted a technique using coldspray ioniza- detected. Furthermore, ESI positive ion detection of
tion (CSI)-MS, which was recently developed by Yama- PhIˆO/KBr in water showed that the activated species
guchi et al.,[ since disproportionation of PhIˆOseems
15]
form oligomeric structures probably due to hydrophobic
to occur readily under normal ionization conditions effects. Generation of Br was not detected under the
2
Adv. Synth. Catal. 2002, 344, 328 ± 337
331

FULL PAPERS
Yasuyuki Kita et al.
Figure 3. Detection of analogous reactive intermediates of (p-MeOC H )IˆO/KBr by ESI-MS.
6
4
conditions for ESI-MS measurement, although detec- activation of PhIˆOwith KBr involving 4 is very
tion of Br2 was reported when phenyliodine(III) different from the mechanism involving transition
diacetate (PIDA) had been reacted with TMSBr in metals or TEMPO, because in the latter cases, the metal
[11b]
CH Cl .
Therefore, at present, on the basis of above- oxide or N-oxoammonium salt functions as the reactive
2
2
mentioned experimental results and ESI-MS, the re- species.
agent containing an I-Br bond forms the reactive
intermediate, while it is not clear whether I(III), Br(I),
or mixed-valent iodine species are more likely to be the Environmentally Benign Oxidation Reactions using a
±
actual reactive intermediate. I(I) [I (Br) ] species sim- Polymer-Supported I(III) Reagent, PDAIS
2
16]
[
ilar to that reported by Kirschning et al. also seemed
to be a possible reactive intermediate from the basis of Next, we modified this system to develop a practical and
±
the ESI-MS. However, I (Br)2 was found to be a clean procedure for the oxidation of alcohols using a
decomposed product since a stoichiometric amount of polymer-supported hypervalent iodine(III) reagent.
PhI was always generated from the reactions, and Solid and polymer-supported reagents have applica-
polyiodostyrene was recovered quantitatively in the tions in combinatorial chemistry, and the uses of such
oxidation using PDAIS. In fact, the peak corresponding operationally simple and environmentally benign re-
±
to I (Br) appeared on allowing the reaction solution to agents are becoming more and more important in the
2
stand for 2 h (Figure 2, c). Accordingly, in the presence pharmaceutical and agrochemical industries. Several
of alcohols 1, the reaction of 1 with 4 is expected to occur polymer-bound oxidants have been reported,[ and
17]
±
immediately without generating I (Br) .
polymer-supported hypervalent iodine reagents should
2
Finally, a plausible reaction mechanism for the be a welcome addition due to their versatility, low
[
18]
catalytic activation of PhIˆOwith KBr was deduced,
toxicity, and high yields. Recently, Togo et al., Ley et
[
19]
[20]
and is depicted in Scheme 1. In this mechanism, al., and we demonstrated that both poly(diacetoxy-
polymeric iodosobenzene is initially decomposed to an iodo)styrene (PDAIS) and polybis(trifluoroacetoxy-
[
21]
[
19b,20a]
oligomeric form by the addition of KBr to form the iodo)styrene (PBTIS)
show similar reactivity to
highly reactive intermediate 4. Then, 4 reacts with phenyliodine(III) diacetate (PIDA) and phenylio-
alcohols 1 to yield the corresponding carboxylic acids or dine(III) bis(trifluoroacetate) (PIFA), respectively,
ketones with regeneration of KBr. This suggests that the and utilized them in organic solvents as a replacement
for the previously reported iodine(III) reagents. A
method for the oxidation of alcohols using DMP with
a thiosulfate resin was recently reported by Parlow et
[
22]
al. but this required an excess amount of reagent. We
re-examined the oxidation using PDAIS in water. The
oxidation of saturated secondary alcohols using
+
–
cat. X Br
–
+
O X
–
+
O X
I
O
1.1 equivalents of PDAIS and 0.2 equivalents of KBr
Ph
I
Ph
I
H
Ph
n
1
2
R2
proceeded in water at room temperature in a few hours
to give the corresponding carbonyl compounds 2 in
excellent yields (Table 3). In the oxidation of primary
alcohols, the reaction rate was remarkably enhanced by
heating at 80 8C (entries 8 ± 11, Table 3). The present
Br HOCH(R )R
O
C
R1
4
(
PhI=O)
PhI
H2O
Reactive
1
Intermediate
X: K or oligomelic iodine species)
(
1
2
R R C=O
2
Scheme 1. A plausible reaction mechanism for the oxidation reaction was also found to be applicable to the oxidation
of alcohols.
of diols to the corresponding lactones (entries 12 ± 14,
332
Adv. Synth. Catal. 2002, 344, 328 ± 337

Oxidation of Alcohols in Water Using Hypervalent Iodine(III) Reagents
FULL PAPERS
Table 3. Oxidation of alcohols 1 (see Figure 1) with PDAIS/KBr in H O.
2
I(OAc)2-KBr
H2O
Ketones (2) or
Carboxylic Acids (2)
or Lactones (3)
Alcohols (1)
Entry
Substrate
Product
KBr [equiv.]
Time [h]
Yield [%][a]
c]
1
2
3
4
5
6
7
8
9
0
1
2
3
4
1a
1d
1e
1e
1e
1g
1i
1k
1n
1o
1p
1q
1r
2a
2d
2e
2e
2e
2g
2i
2k
2n
2o
2p
3b
3c
3g
0.2
0.2
0.2
0.2
0.2
0.2
0.2
1.0
1.0
1.0
1.0
1.0
1.0
1.0
24
4
7
7
7
quant.[
quant.[
b, c]
[
b, c]
quant.
93[ (cycle 2)
b, c]
91[ (cycle 3)
b, c]
[
b, c]
3
86
b, c]
20
12
7
8
10
3
86[
91[
b, d,e, f]
d, e,f]
d, e,f]
d, e,f]
d]
[
92
1
1
1
1
1
74[
82[
88[
[d]
12
10
quant.
b, d]
1u
93[
[
[
[
[
[
[
a]
Yields are an average of two or more runs. Isolated yields unless otherwise noted.
Yields were determined by GC.
b]
c]
d]
e]
f]
1
2
.1 equivalents of PDAIS were used.
.5 equivalents of PDAIS were used.
Small amount of ester was also obtained by oxidative condensation.
Reaction was carried out at 80 8C.
Table 3). Furthermore, the iodinated resin could be expansion of the method using a polymer-supported
regenerated and recycled successfully without loss of I(III) reagent, PDAIS, enabled recycling of the oxidant
activity (entries 3 ± 5, Table 3). We also unexpectedly as well as facile work-up. The present procedure will
found that water is asuitable solvent for PDAIS-induced provide a facile and environmentally benign method for
oxidation, and that PDAIS has considerable stability in the catalytic activation of a variety of sluggishly reactive
water.[ Since both water and Br are indispensable for and/or sparsely soluble hypervalent iodine reagents in
23]
±
[
24]
reaction progression,
this reaction might also be water under neutral conditions.
proceeding via a reactive intermediate similar to 4
formed by ligand exchange of diacetate. However,
considering that the reactivity of PDAIS is similar to
that of PIDA, the mechanism via the formation of
bromate(I) complex or BrOAc might also be possi-
ble.[
Experimental Section
16b,24]
General Remarks and Starting Materials
The positive features of the use of PDAIS are
summarized as follows: 1) ease of operation; 2) facile
recyclability of the polymer-supported iodine(III) re-
agent; ease of re-oxidation of the recovered resin
All melting points are uncorrected. Infrared (IR) absorption
±1
spectra (cm ) were recorded on a Shimadzu FTIR-8400
1
13
instrument. H NMR (and C NMR) spectra were recorded
on JEOL JNM-EX 300 and JEOL JNM-EX 270 spectrometers
with TMS as an internal standard. Analytical gas chromatog-
(
polyiodostyrene) with peracetic acid (30% H O and
2 2
Ac O) and repeated use without loss of activity; 3) raphy (GC) was carried out on a Shimadzu GC-1700 gas
2
excellent yields; 4) environmental consciousness, such chromatograph with an HP-5 column (0.32 mm  30 m, cross-
that no organic solvent is used in the reaction and only a linked 5% PH ME siloxane, Hewlett Packard) using helium as
carrier gas. ESI-MS was carried out on a JEOL JMS-LCmate.
small amount is needed in the work-up.
Merck silica gel 60 was used for column chromatography, and
E. Merck pre-coated TLC plates and silica gel F254 were used
for preparative thin-layer chromatography. PhIˆOwas pur-
Conclusions
chased from Tokyo Chemical Industry Co., Ltd. (TCI). Other
commercially available compounds 1a ± e, 1g, 1i ± n, 1p, 1r, 1t ±
We have achieved a clean and efficient oxidation of
alcohols using a mild and non-toxic oxidant, PhIˆO,
x, and KBr were purchased from Aldrich and TCI, and were
[25]
[26]
used without further purification. Compounds 1f,
1o,
with KBr in water, and were able to detect the reactive 1q,[ and 1s were prepared according to known procedures.
27]
[28]
intermediates by ESI-MS for the first time. Further Compound 1h was prepared by tosylation of 4,4-piperidinediol
Adv. Synth. Catal. 2002, 344, 328 ± 337
333

FULL PAPERS
Yasuyuki Kita et al.
hydrochloride, followed by reduction with sodium borohy- General Procedure for Oxidation of Secondary
dride. Oxidation products 2a ± e, 2g, 2i ± n, 2p, 3b, 3e, 3g ± j were
ˆ
Alcohols using PhI O/KBr
identified by comparison with commercial samples. The known
products 2f,[ 2o, 3c, 3d, and 3f were characterized by
25]
[29]
[30]
[31]
[30]
H O(2.0 mmol) was added dropwise to a stirred mixture of
2
secondary alcohols 1e ± j (0.2 mmol), PhIˆO(24.2 mg,
comparing their spectral and physical data with the literature
values. Poly(diacetoxyiodo)styrene, PDAIS, was prepared by
0
.22 mmol), and KBr (23.8 mg, 0.2 mmol). The mixture was
known procedures.[
18a,21a]
stirred or sonicated for several hours while checking the
reaction progress by gas or thin-layer chromatography. After
completion, n-hexane was added, the mixture was dried over
Na SO , and then filtered. Evaporation of the solvent under
vacuum afforded a crude product that was further purified by
column chromatography [Et O(or AcOEt)/ n-hexane] to give
A few corrections of both the reaction conditions and yields
have been made in the oxidation of primary alcohols with
PDAIS as well as PhIˆO, because the ratio of carboxylic acid to
2
4
ester was variable (that is, ester was sometimes obtained by an
oxidative condensation reaction in > 40% yield) and depend-
ed upon the efficiency of stirring under our previous con-
2
pure 2e ± j in the yields listed in Table 1. Yields of 2e,g,i were
determined by gas chromatography.
ditions.[6] Therefore, we re-examined and optimized the
[
25]
5
-Benzoyloxy-2-hexanone (2f):
Colorless oil; yield:
reaction conditions leading to a more reliable and reproducible
oxidation of primary alcohols.
1
quant.; H NMR (CDCl ): d ˆ 1.28 (d, J ˆ 6.1 Hz, 3H), 1.91
3
-Benzoyloxy-2-hexanol (1f):[
25]
Colorless oil; 1H NMR
(q, J ˆ 7.6 Hz, 2H), 2.07 (s, 3H), 2.48 (dd, J ˆ 7.6, 6.7 Hz, 2H),
5
5
7
.09 (q, J ˆ 6.1 Hz, 1H), 7.37 (dd, J ˆ 7.6, 7.3 Hz, 2H), 7.46 ±
(
1
CDCl ): d ˆ 1.21 (d, J ˆ 6.2 Hz, 3H), 1.36 (d, J ˆ 6.2 Hz, 3H),
3
1
3
.52 (m, 1H), 7.96 (dd, J ˆ 7.0, 1.5 Hz, 2H); C NMR (CDCl ):
.52 ± 1.86 (m, 6H), 3.83 (m, 1H), 5.16 ± 5.20 (m, 1H), 7.29 ± 7.57
3
d ˆ 20.2, 29.8, 30.0, 39.5, 70.9, 128.3, 129.5, 130.4, 132.9, 166.1,
(
1
m, 3H), 8.03 ± 8.05 (m, 2H); IR (KBr): nÄ ˆ 3371, 2972, 1713,
±1
±1
‡
207.9; IR (KBr): nÄ ˆ 1726, 1717, 1277, 1133, 714 cm ;
277, 712 cm ; MS: m/z ˆ 222 [M ], 123, 105, 77; HRFABMS:
‡
‡
HRFABMS: m/z calcd. for C H O (M ‡ H): 221.1178;
m/z calcd. for C H O (M ‡ H): 223.1334; found: 223.1317.
13 17
3
13
19
3
found: 221.1154.
1-(4-Toluenesulfonyl)tetrahydro-4(1H)-pyridinone (2h):
1
-(4-Toluenesulfonyl)-4-piperidinol (1h): Colorless crystals;
1
mp 130 ± 132 8C (Et O); H NMR (CDCl ): d ˆ 1.37 (d, J ˆ
2
3
1
Colorless crystal; yield: 86%; mp 121 8C (Et O); H NMR
4
3
7
3
.2 Hz, 1H), 1.58 ± 1.71 (m, 2H), 1.90 ± 1.96 (m, 2H), 2.43 (s,
H), 2.81 ±2.88 (m, 2H), 3.27 ± 3.35 (m, 2H), 3.74 ±3.78 (m, 1H),
.32 (d, J ˆ 8.2 Hz, 2H), 7.65 (d, J ˆ 8.2Hz, 2H); IR (KBr): nÄ ˆ
2
(
CDCl ): d ˆ 2.35 (s, 3H), 2.42 ± 2.47 (m, 4H), 3.27 ± 3.32 (m,
3
1
3
4
H), 7.26 (d, J ˆ 8.2 Hz, 2H), 7.59 (d, J ˆ 8.2 Hz, 2H); C NMR
±1
‡
(CDCl ): d ˆ 21.6, 40.7, 45.9, 127.4, 129.8, 133.3, 144.0, 205.4;
557, 2930, 1307, 1165, 729 cm ; MS: m/z ˆ 255 [M ]; anal.
3
±1
IR (KBr): nÄ ˆ 1717, 1362, 1337, 1165, 725 cm ; MS: m/z ˆ 253
calcd. for C H NO S: C 56.45, H 6.71, N 5.49, S 12.56%;
12
17
3
‡
(
M ), 98; anal. calcd. for C H NO S: C 56.90, H 5.97, N 5.53, S
found: C 56.40, H 6.63, N 5.43, S 12.53%.
12 15
3
-Azido-1-hexanol (1o):[ Colorless oil; H NMR (CDCl ):
26]
1
12.66%; found: C 56.87, H 5.93, N 5.55, S 12.67%.
6
3
d ˆ 1.38 ± 1.42 (m, 4H), 1.54 ± 1.63 (m, 4H), 3.24 ± 3.27 (m, 2H),
3
1
1
.62 ± 3.65 (m, 2H); IR (KBr): nÄ ˆ 3329, 2936, 2097, 1258,
±
1
‡
057 cm ; HRFABMS: m/z calcd. for C H N O (M ‡ H): General Procedure for Oxidation of Primary Alcohols
6
14
3
44.1137; found: 144.1142.
1
using PhIˆO/KBr
,2-Benzenedimethanol (1q):[ Colorless crystal; mp 64 ±
27]
1
A suspension of PhIˆO(132.0 mg, 0.6 mmol) and KBr
6
(
6 8C (Et O) (Lit. mp 64 ± 65 8C); H NMR (CDCl ): d ˆ 3.25
2
3
(
23.8 mg, 0.2 mmol) in H O(10 mL) was stirred for a few
2
br s, 1H), 4.70 (s, 4H), 7.32 (s, 4H); IR (KBr): nÄ ˆ 3287, 2882,
±
1
‡
minutesatroom temperature, then sonicatedfor afew minutes.
Then, primary alcohol 1k ± p (0.2 mmol) was added to the
mixture with stirring. After completion, AcOEt was added to
the reaction mixture, then the mixture was acidified by a small
amount of 1 N HCl, extracted with AcOEt, dried, and
evaporated. The residue was purified by column chromatog-
raphy onsilica gel (AcOEt/n-hexane) to give 2k±p inthe yields
listed in Table 1. Yields of 2k ± l were determined by gas
1
454, 1005, 752 cm ; MS: m/z ˆ 138 [M ], 120, 91, 77.
[28]
2
-Hydroxymethylphenethyl alcohol (1s): Colorless oil;
1
H NMR (CDCl ): d ˆ 2.94 (t, J ˆ 5.9 Hz, 2H), 3.88 (t, J ˆ
3
5
3
.9 Hz, 2H), 4.64 (s, 2H), 7.22 ± 7.33 (m, 4H); IR (KBr): nÄ ˆ
±1 ‡
317, 2880, 1015, 750 cm ; MS: m/z ˆ 152 [M ], 134, 104, 77.
chromatography.
-Azido-1-hexanoic Acid (2o):[ Colorless oil; yield: 70%
29]
6
1
(
PhIˆO); 74% (PDAIS); H NMR (CDCl ): d ˆ 1.34 ± 1.42 (m,
3
2
H), 1.51 ±1.61 (m, 4H), 2.29 ± 2.34 (m, 2H), 3.19 ±3.24 (m, 2H);
C NMR (CDCl ): d ˆ 24.1, 26.1, 28.5, 33.7, 51.2, 179.0; IR
General Procedure for Oxidation of Benzylic Alcohols
using PhIˆO/KBr
1
3
3
±1
(
KBr): nÄ ˆ 2869, 2099, 1715, 1456, 1258 cm ; HRFABMS: m/z
‡
H O(2.0 mmol) was added dropwise to a stirred mixture of
calcd. for C H N O (M ‡ H): 158.0935; found: 158.0928.
2
6
12
3
2
allylic or benzylic alcohols 1a ± d (0.20 mmol) and PhIˆO
(
0.50 mmol for 1a; 0.22 mmol for 1b ± d). The mixture was
stirred or sonicated for several hours while checking the
reaction progress by gas or thin-layer chromatography. After
completion, n-hexane (or AcOEt for 1a) was added, the
mixture was dried over Na SO , and then filtered. Evaporation
General Procedure for Oxidation of Diols to Lactones
using PhIˆO/KBr
H O(2.0 mmol) was added dropwise to a stirred mixture of
2
4
2
of the solvent under vacuum afforded a crude product that was
diol 1q ± x (0.2 mmol), PhIˆO(110.0 mg, 0.5 mmol), and KBr
(23.8 mg, 0.2 mmol). The mixture was stirred or sonicated for
several hours while checking the reaction progress by gas or
thin-layer chromatography. After completion, n-hexane (or
further purified by column chromatography (Et O/n-hexane)
2
to give pure 2a ± d in the yields listed in Table 1. Yields of 2b ± d
were determined by gas chromatography.
334
Adv. Synth. Catal. 2002, 344, 328 ± 337

Oxidation of Alcohols in Water Using Hypervalent Iodine(III) Reagents
FULL PAPERS
AcOEt) was added, the mixture was dried over Na SO , and
then filtered. Evaporation of the solvent under vacuum
afforded a crude product that was further purified by column
hours. After work-up A or B, the respective product 2 was
obtained.
2
4
Work-up A: After completion, the reaction mixture was
acidified by 1 N HCl, and filtered. The residue was washed with
AcOEt and a small amount of MeOH, then the filtrate was
extracted with AcOEt, dried and evaporated. The residue was
purified by column chromatography (AcOEt/n-hexane) to
give 2.
chromatography [Et O(or AcOEt)/ n-hexane] to give pure 3b
2
±
j in the yields listed in Table 2. Yields of 3g ± j were
determined by gas chromatography.
cis-Hexahydrophthalide (3c):[ Colorless oil; yield: quant.;
30]
1
H NMR (CDCl ): d ˆ 1.13 ± 1.19 (m, 3H), 1.53 ± 1.75 (m, 4H),
3
2
4
2
1
.02 ± 2.07 (m, 1H), 2.41 ± 2.57 (m, 2H), 3.88 (d, J ˆ 8.9 Hz, 1H),
Work-up B: After completion, the reaction mixture was
1
3
TM
.13 (dd, J ˆ 6.9, 4.9 Hz, 1H); C NMR (CDCl ): d ˆ 22.4, 22.8,
filtered through abselut NEXUS (Varian) to remove aque-
3
3.4, 27.1, 35.3, 39.4, 71.7, 178.5; IR (KBr): nÄ ˆ 2859, 1790, 1375,
ous KBr. Then, the polymer residue was washed (extracted)
with MeOH, the filtrate was evaporated, and purified by
column chromatography (AcOEt/n-hexane) to give 2.
±1
‡
130, 914 cm ; MS: m/z ˆ140 [M ], 95, 85, 80, 69, 55.
Isochroman-1-one (3d):[
31]
Colorless oil; yield: 70%;
1
H NMR (CDCl ): d ˆ 2.97 (t, J ˆ 5.8 Hz, 2H), 4.44 (t, J ˆ
3
5
7
(
1
.8 Hz, 2H), 7.18 (d, J ˆ 7.6 Hz, 1H), 7.30 (t, J ˆ 7.6 Hz, 1H),
13
.45 (t, J ˆ 7.6 Hz, 1H), 7.99 (d, J ˆ 7.6 Hz, 1H); C NMR
CDCl ): d ˆ 27.6, 67.2, 125.1, 127.1, 127.5, 130.1, 133.5, 139.4,
3
±1
‡
General Procedure for Oxidation of Secondary and
65.0; IR (KBr): nÄ ˆ 1717, 1244 cm ; MS: m/z ˆ 148 [M ].
,8-Naphthalide (3f):[ Yellow crystals; yield: 92%; mp 153
30]
Benzylic Alcohols using PDAIS/KBr in H O
1
2
1
±
155 8C (Lit. mp 154.5 ± 156.0 8C); H NMR (CDCl ): d ˆ 5.83
3
PDAIS (8.5 mmol) was added to a stirred suspension of 1
(
s, 2H), 7.36 ± 7.38 (m, 1H), 7.53 ± 7.58 (m, 1H), 7.62 ± 7.67 (m,
(
7.7 mmol) and KBr (183.2 mg, 1.5 mmol) in H O(40 mL), and
2
1
H), 7.85 (d, J ˆ 8.4 Hz, 1H), 8.11 (d, J ˆ 8.3 Hz, 1H), 8.39 (d,
the mixture was then stirred at room temperature for several
hours. After completion, the reaction mixture was filtered and the
residue containing 2 was washed with a small amount of water
to remove KBr, then extracted with n-hexane or MeOH, and
the filtrate was evaporated to give 2. The product was purified
by column chromatography, when necessary. In some cases, the
use of BOND ELUT C2 or C8 (Varian) for filtration was
effective for preventing leakage of 2 when washing the residue.
13
J ˆ 7.2 Hz, 1H); C NMR (CDCl ): d ˆ 69.9, 120.0, 121.3,
3
1
26.3, 126.5, 128.1, 128.9, 131.8, 133.3; IR (KBr): nÄ ˆ 1720, 1244,
1
±1 ‡
086, 775 cm ; MS: m/z ˆ 184 [M ], 155, 127.
Iodination of Polystyrene
A mixture of polystyrene (5 g) (MWˆ 44,000, purchased from
Aldrich), iodine (5 g), diiodine pentaoxide (2 g), carbon
tetrachloride (10 mL), and 50% sulfuric acid (10 mL) in
nitrobenzene (30 mL) was stirred at 90 8C for 60 h. The
reaction mixture was precipitated by adding AcOEt General Procedure for Oxidation of Diols using
(
100 mL) and filtered. The residue was washed with AcOEt PDAIS/KBr in H O
2
and methanol. The resulting solid was collected and dried
under vacuum to give poly(4-iodostyrene); yield: 10.3 g.
Elemental analysis (C 43.87, H 3.36, I 51.65%) revealed the
resin loading to be 4.069 mmol g , which indicated that 87% of
the phenyl rings in polystyrene were iodinated.
H O(10 ± 20 mmol) was added dropwise to a stirred mixture of
2
diol 1q, r, u (1.6 mmol), PDAIS (4.0 mmol), and KBr
(1.6 mmol). The mixture was stirred or sonicated for several
hours while checking the reaction progress by gas or thin-layer
chromatography. After completion, the reaction mixture was
filtered and extracted with n-hexane or AcOEt, and the filtrate
was dried, evaporated, and purified by column chromatogra-
phy to give 3b, c, g. In some cases, the use of BOND ELUT C2
or C8 (Varian) for filtration was effective for preventing
leakage of 2 when washing the residue.
±1
Preparation of PDAIS
Hydrogen peroxide (30%, 64.4 mL) was added dropwise to
acetic anhydride (233.6 mL) at 0 8C. The solution was slowly
warmed to room temperature and stirred overnight. To this
solution, poly(4-iodostyrene) (8.59 g) was added. Then, stir-
ring was continued at 40 8C overnight. Et Owas added to the
2
reaction mixture and the whole was filtered. The residue was
ESI-MS Experiment
washed with Et Oto give PDAIS; yield: 12.6 g. Elemental
2
analysis (C 38.35, H 3.57, I 38.39%) revealed the resin loading
ESI-mass spectra were measured by a modification of the CSI-
MS technique. Typical measurement conditions for ESI-MS
are as follows: acceleration voltage; 2.5 kV, orifice voltage; 0 V,
resolution (10% valley definition); 1500, sample flow; 20 mL/
min, solvent; water, the temperature of desolvation chamber
±1
[15]
to be 2.172 mmol g , which indicated that 72% of the 4-
iodophenyl rings in the resin were converted into 4-(diacetoxy-
iodo)phenyl rings. PDAIS was used without any pretreatment.
(
with cooling by pouring liquid nitrogen under the heater on to
prevent freezing water); 30 8C.
General Procedure for Oxidation of Primary Alcohols
The sample was prepared as follows; PhIˆO(0.02 mmol)
using PDAIS/KBr in H O
2
was added to a solution of KBr (0.02 mmol) in H O(1 mL) at
2
PDAIS (5.0 mmol) was added to a vigorously stirred suspen-
room temperature. The mixture (suspension) was sonicated for
a few minutes. After centrifugation, the supernatant was
sion of 1 (2.0 mmol) and KBr (238 mg, 2.0 mmol) in H O
2
(
80 mL) at 80 8C, and the mixture was stirred for several
diluted with H O(1 mL) to yield the sample.
2
Adv. Synth. Catal. 2002, 344, 328 ± 337
335

FULL PAPERS
Yasuyuki Kita et al.
Acknowledgements
[9] a) P. A. Grieco, (Ed.), Organic Synthesis in Water, Black-
ie Academic, London, 1998; b) B. Cornils, W. A. Herr-
mann, (Eds.), Aqueous-Phase Organometallic Catalysis,
Wiley-VCH, Weinheim, 1998; c) C.-J. Li, T.-H. Chan,
This work was supported by the Grant-in-Aid for Scientific
Research (S) (No. 13853010) and for Encouragement of Young
Scientists (No. 13771331) from the Ministry of Education,
Science, Sports and Culture, Japan. HT also thanks the Hoh-
ansha Foundation for a research fellowship.
(Eds.) Organic Reactions in Aqueous Media, John Wiley,
New York, 1997.
[
10] a) H. Tohma, S. Takizawa, H. Watanabe, Y. Kita,
Tetrahedron Lett. 1998, 39, 4547 ± 4550; b) H. Tohma, S.
Takizawa, H. Watanabe, Y. Fukuoka, T. Maegawa, Y.
Kita, J. Org. Chem. 1999, 64, 3519 ± 3523.
11] The effects of halide ion have been reported by several
groups; a) T. Shono, Y. Matsumura, J. Hayashi, M.
Mizoguchi, Tetrahedron Lett. 1979, 165 ± 168; b) P. A.
Evans, T. A. Brandt, J. Org. Chem. 1997, 62, 5321 ± 5326;
c) S. D. Rychnovsky, R. Vaidyanathan, J. Org. Chem.
References and Notes
[
[
1] a) K. Sato, M. Aoki, J. Takagi, R. Noyori, J. Am. Chem.
Soc. 1997, 119, 12386 ± 12387; b) I. E. Mark o¬ , M. Tsuka-
zaki, P. R. Giles, S. M. Brown, C. J. Urch, Angew. Chem.
Int. Ed. Engl. 1997, 36, 2208 ± 2210; Angew. Chem. 1997,
1
999, 64, 310 ± 312; d) J. H. Espenson, Z. Zhu, T. H.
1
1
09, 2297 ± 2299; c) K. Sato, M. Aoki, R. Noyori, Science
998, 281, 1646 ± 1647; c) M. Zhao, J. Li, E. Mano, Z.
Zauche, J. Org. Chem. 1999, 64, 1191 ± 1196; e) H.
Tohma, S. Takizawa, H. Morioka, T. Maegawa, Y. Kita,
Chem. Pharm. Bull. 2000, 48, 445 ± 446.
Song, D. M. Tschaen, E. J. J. Grabowski, P. J. Reider, J.
Org. Chem. 1999, 64, 2564 ± 2566; d) G. ten Brink,
I. W. C. E. Arends, R. A. Sheldon, Science 2000, 287,
[
12] a) E. J. Corey, A. Palani, Tetrahedron Lett. 1995, 36,
7
945 ± 7948; b) J. M. Bueno, J. M. Coter o¬ n, J. L. Chiara,
1
636 ± 1639, and references cited therein.
A. Fern a¬ ndez-Mayoralas, J. M. Fiandor, N. Valle, Tetra-
hedron Lett. 2000, 41, 4379 ± 4382; c) J. Roels, P. Metz,
Synlett 2001, 789 ± 790.
[
2] Recent reviews see: a) P. J. Stang, V. V. Zhdankin, Chem.
Rev. 1996, 96, 1123 ± 1178; b) A. Varvoglis, Hypervalent
Iodine in Organic Synthesis, Academic Press, San Diego,
[
[
[
[
13] The reaction took longer (24 h) to complete when the
1997; c) T. Kitamura, Y. Fujiwara, Org. Prep. Proc. Int.
1997, 29, 409 ± 458; d) T. Wirth, U. H. Hirt, Synthesis
1999, 1271 ± 1287.
concentration of 1u in water was 0.2 M.
14] H. W. Richter, B. R. Cherry, T. D. Zook, G. F. Koser, J.
Am. Chem. Soc. 1997, 119, 9614 ± 9623.
15] S. Sakamoto, M. Fujita, K. Kim, K. Yamaguchi, Tetrahe-
dron 2000, 56, 955 ± 964.
16] a) A. Kirschning, H. Monenschein, C. Schmeck, Angew.
Chem. Int. Ed. 1999, 38, 2594 ± 2596; Angew. Chem. 1999,
[
[
3] a) D. B. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155 ±
4
156; b) S. D. Meyer, S. L. Schreiber, J. Org. Chem. 1994,
5
9, 7549 ± 7552.
4] a) M. Frigerio, M. Santagostino, S. Sputore, G. Palm-
isano, J. Org. Chem. 1995, 60, 7272 ± 7276; b) E. J. Corey,
A. Palani, Tetrahedron Lett. 1995, 36, 3485 ± 3488; c) T.
Wirth, Angew. Chem. Int. Ed. 2001, 40, 2812 ± 2814;
Angew. Chem. 2001, 113, 2889 ± 2892.
1
11, 2720 ± 2722; b) H. Monenschein, G. Sourkouni-
Argirusi, K. M. Schubothe, T. O×Hare, A. Kirschning,
Org. Lett. 1999, 1, 2101 ± 2104.
[
17] Reviews see: a) S. V. Ley, I. R. Baxendale, R. N. Bream,
P. S. Jackson, A. G. Leach, D. A. Longbottom, M. Nesi,
J. S. Scott, R. I. Storer, S. J. Taylor, J. Chem. Soc. Perkin
Trans. 1, 2000, 3815 ± 4195; b) G. Bhalay, A. Dunstan, A.
Glen, Synlett 2000, 1846 ± 1859; c) A. Kirschning, H.
Monenschein, R. Wittenberg, Angew. Chem. Int. Ed.
[
5] Our recent work: a) Y. Kita, H. Tohma, K. Hatanaka, T.
Takada, S. Fujita, S. Mitoh, H. Sakurai, S. Oka, J. Am.
Chem. Soc. 1994, 116, 3684 ± 3691; b) Y. Kita, M.
Arisawa, M. Gyoten, M. Nakajima, R. Hamada, H.
Tohma, T. Takada, J. Org. Chem. 1998, 63, 6625 ± 6633;
c) T. Takada, M. Arisawa, M. Gyoten, R. Hamada, H.
Tohma, Y. Kita, J. Org. Chem. 1998, 63, 7698 ± 7706; d) Y.
Kita, M. Egi, T. Takada, H. Tohma, Synthesis 1999, 885 ±
2
001, 40, 650 ± 679; Angew. Chem. 2001, 113, 670 ± 701.
18] a) H. Togo, G. Nogami, M. Yokoyama, Synlett 1998,
34 ± 536; b) H. Togo, S. Abe, G. Nogami, M. Yokoyama,
[
[
5
8
97; e) M. Arisawa, S. Utsumi, M. Nakajima, N. G.
Ramesh, H. Tohma, Y. Kita, Chem. Commun. 1999,
69 ± 470, and references cited therein.
Bull. Chem. Soc. Jpn. 1999, 72, 2351 ± 2356.
19] a) S. V. Ley, A. W. Thomas, H. Finch, J. Chem. Soc.
Perkin Trans. 1 1999, 669 ± 671; b) S. V. Ley, O. Schucht,
A. W. Thomas, P. J. Murray, J. Chem. Soc. Perkin Trans. 1
1999, 1251 ± 1252. They obtained benzaldehyde quanti-
tatively, however, only a trace amount of 2e was obtained
even after 48 h under their reaction conditions (PDAIS
4
[6] H. Tohma, S. Takizawa, T. Maegawa, Y. Kita, Angew.
Chem. Int. Ed. 2000, 39, 1306 ± 1308; Angew. Chem. 2000,
1
12, 1364 ± 1368.
7] a) P. M¸ller, J. Godoy, Tetrahedron Lett. 1981, 22, 2361 ±
364; b) T. Yokoo, K. Matsumoto, K. Oshima, K.
[
2
Utimoto, Chem. Lett. 1993, 571 ± 572; c) W. Adam, S.
Hajra, M. Herderich, C. R. Saha-Mˆller, Org. Lett. 2000,
in CH Cl ).
2 2
[20] a) H. Tohma, H. Morioka, S. Takizawa, M. Arisawa, Y.
Kita, Tetrahedron 2001, 57, 345 ± 352; b) H. Tohma, H.
Morioka, Y. Harayama, M. Hashizume, Y. Kita, Tetra-
hedron Lett. 2001, 42, 6899 ± 6902.
[21] The method for preparing PDAIS was originally report-
ed by Okawara in 1961, and was also reported inde-
pendently by Hallensleben; a) M. Okawara, K. Mizuta,
2
, 2773 ± 2776; d) A. De Mico, R. Margarita, L. Parlanti,
A. Vescovi, G. Piancatelli, J. Org. Chem. 1997, 62, 6974 ±
977.
8] a) T. Takaya, H. Enyo, E. Imoto, Bull. Chem. Soc. Jpn.
968, 41, 1032; b) R. S. Varma, R. Dahiya, R. K. Saini,
Tetrahedron Lett. 1997, 38, 7029 ± 7032.
6
[
1
336
Adv. Synth. Catal. 2002, 344, 328 ± 337

Oxidation of Alcohols in Water Using Hypervalent Iodine(III) Reagents
FULL PAPERS
Kogyo Kagaku Zasshi 1961, 64, 232 ± 235; b) Y. Yamada,
M. Okawara, Makromol. Chem. 1972, 152, 153 ± 162;
c) M. L. Hallensleben, Angew. Makromol. Chem. 1972,
W. C. Shakespeare, P. A. Sprengeler, P. Hamley, A. B.
Smith III, T. Reisine, K. Raynor, L. Maechler, C.
Donaldson, W. Vale, R. M. Freidinger, M. R. Cascieri,
C. D. Strader, J. Am. Chem. Soc. 1993, 115, 12550 ±
12568.
2
7, 223 ± 227.
22] J. J. Parlow, B. L. Case, M. S. South, Tetrahedron 1999,
5, 6785 ± 6796.
[
[
5
[27] H. C. Brown, S. Narasimhan, Y. M. Choi, J. Org. Chem.
1982, 47, 4702 ± 4708.
23] Even after stirring PDAIS in water for 4 days, the
addition of 1e and KBr to this suspension gave 2e in 68%
yield.
[28] R. Annunziata, M. Cinquini, F. Cozzi, P. Giaroni, M.
Benaglia, Tetrahedron 1991, 47, 5737 ± 5758; H. L. Hol-
land, M. Kindermann, S. Kumaresan, T. Stefanac,
Tetrahedron Asymmetry 1993, 4, 1353 ± 1364.
[29] D. Charon, M. Mondange, J-F. Pons, K. L. Blay, R.
Chaby, Bioorg. Med. Chem. 1998, 6, 755 ± 765.
[30] S-I. Murahashi, T. Naota, K. Ito, Y. Maeda, H. Taki, J.
Org. Chem. 1987, 52, 4319 ± 4327.
[
24] The yield of 2e was only 8% when the reaction was
performed with PDAIS in CH Cl (containing MS 4 ä)
2
2
‡
±
in the presence of 20 mol % Et N Br as a bromide ion
4
source. However, addition of a catalytic amount of water
to the above-mentioned mixture enhanced the yield of
2
e to 51%.
[
25] J. Ishiyama, S. Maeda, K. Takahashi, Y. Senda, S,
Imaizumi, Bull. Chem. Soc. Jpn. 1987, 60, 1721 ± 1726.
26] R. Hirschmann, K. C. Nicolaou, S. Pietranico, E. M.
Leahy, J. Salvino, B. Arison, M. A. Cichy, P. G. Spoors,
[31] J. Lehmann, M. Nieger, T. Witt, Heterocycles 1994, 38,
511 ± 528.
[
Adv. Synth. Catal. 2002, 344, 328 ± 337
337