Catalytic oxidation of alcohols to corresponding aldehydes or ketones with TEMPO-mediated iodosobenzene in water in the presence of a surfactant

Article abstract of DOI:10.1080/00397910903219427

An efficient, facile, and rapid oxidation of alcohols to the corresponding aldehydes or ketones with a stoichiometric amount of iodosobenzene (PhIO) in the presence of catalytic amounts of 2,2,6,6-tetramethyl-1-piperidinyloxyl free radical (TEMPO), KBr, a

Full text of DOI:10.1080/00397910903219427

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Catalytic Oxidation of Alcohols to
Corresponding Aldehydes or Ketones
with TEMPO-Mediated Iodosobenzene in
Water in the Presence of a Surfactant
Chenjie Zhu a , Yunyang Wei a & Lei Ji a
a School of Chemical Engineering, Nanjing University of Science and
Technology , Nanjing, China
Published online: 17 Jun 2010.
To cite this article: Chenjie Zhu , Yunyang Wei & Lei Ji (2010) Catalytic Oxidation of Alcohols to
Corresponding Aldehydes or Ketones with TEMPO-Mediated Iodosobenzene in Water in the Presence
of a Surfactant, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 40:14, 2057-2066, DOI: 10.1080/00397910903219427
To link to this article: http://dx.doi.org/10.1080/00397910903219427
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Synthetic Communications1, 40: 2057–2066, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903219427
CATALYTIC OXIDATION OF ALCOHOLS TO
CORRESPONDING ALDEHYDES OR KETONES
WITH TEMPO-MEDIATED IODOSOBENZENE IN
WATER IN THE PRESENCE OF A SURFACTANT
Chenjie Zhu, Yunyang Wei, and Lei Ji
School of Chemical Engineering, Nanjing University of Science and
Technology, Nanjing, China
An efficient, facile, and rapid oxidation of alcohols to the corresponding aldehydes or
ketones with a stoichiometric amount of iodosobenzene (PhIO) in the presence of catalytic
amounts of 2,2,6,6-tetramethyl-1-piperidinyloxyl free radical (TEMPO), KBr, and a
surfactant, such as SDS (sodium dodecylsulfate), was reported. The oxidation proceeded
in water at room temperature to afford aldehydes or ketones in excellent yields and high
selectivity without overoxidation to carboxylic acids. Selective oxidation of primary
alcohols in the presence of secondary alcohols was also achieved with the catalytic system
of PhIO/TEMPO/KBr/SDS. A possible mechanism for the oxidation was supposed.
Keywords: Alcohols; iodosobenzene; oxidation; TEMPO; water as solvent
INTRODUCTION
The selective oxidation of alcohols to the corresponding aldehydes or ketones
is a fundamental transformation both in laboratory synthesis and industrial
production.[1] Numerous oxidizing reagents[2] (for example, CrO3, KMnO4, and
MnO2) in stoichiometric amounts have been traditionally employed to accomplish
this transformation but with considerable drawbacks such as the use of expensive
reagents and volatile organic solvents and discharge of environmentally pernicious
wastes. The demands for environmentally benign and ecoconscious chemical pro-
cesses in recent years are encouraging chemists to search for clean, high-yielding,
highly selective, and economical oxidation methods. In the past decade, hypervalent
iodine reagents have become increasingly appreciated by organic chemists for their
mild and highly chemoselective oxidizing properties.[3–6] For example, the widely uti-
lized pentavelent iodine reagents such as Dess–Martin periodinane (DMP)[7–9] and
its precursor 2-iodoxybenzoic acid (IBX)[10–12] oxidize alcohols mildly and efficiently
to carbonyl compounds in excellent yields in organic solvents such as CH2Cl2,
dimethylsulfoxide (DMSO), and acetone. However, these iodine(V) reagents are
potentially explosive because of the organopentavalent iodine structure. Thus, the
Received April 13, 2009.
Address correspondence to Yunyang Wei, School of Chemical Engineering, Nanjing University of
Science and Technology, Nanjing 210094, China. E-mail: ywei@mail.njust.edu.cn
2057

2058
C. ZHU, Y. WEI, AND L. JI
Scheme 1. Oxidation of alcohols catalyzed by PhIO=TEMPO=KBr=SDS in water.
readily available and stable iodine(III) oxidants such as iodosobenzene (PhIO) and
bis(acetoxy)iodobenzene [PhI(OAc)2] attract much attention.
On the other hand, it is well known that nitroxyl radicals, such as
2,2,6,6-tetramethyl-1-piperidinyloxyl free radical (TEMPO), promote oxidation of
various alcohols to the corresponding carbonyl compounds effectively under mild
reaction conditions.[13–18] Recently, De Mico and coworkers reported a mild and
selective method for the oxidation of primary and secondary alcohols using a cata-
lytic amount of TEMPO and bis(acetoxy)iodobenzene [PhI(OAc)2] as a reoxidant.[19]
In contrast to iodine(V)-based reagents and PhI(OAc)2, there are few reports con-
cerning the use of PhIO as a reoxidant for TEMPO.[20,21] Very recently, PhIO was
demonstrated by Tohma et al. to be an effective reagent for the oxidation of alcohols
in aqueous media in the presence of a catalytic amount of potassium bromide.
Although secondary alcohols led to ketones in good yields, primary alcohols were
converted to carboxylic acids, not aldehydes.[22]
In continuation of our interest in exploring systems on the oxidation of organic
compounds,[23] especially alcohols,[24,25] here we report a facile procedure for the
oxidation of alcohols to the corresponding carbonyl compounds with a stoichio-
metric amount of PhIO in the presence of catalytic amounts of TEMPO, KBr,
and a surfactant, such as SDS. The oxidation proceeded in water at room tempera-
ture to afford aldehydes or ketones in excellent yields and high selectivity without
overoxidation to carboxylic acids (Scheme 1).
RESULTS AND DISCUSSION
Oxidation of 4-Nitrobenzyl Alcohol with PhIO/TEMPO/KBr/
Surfactants
Because of the polymeric structure of PhIOn, which makes it insoluble in most
organic solvents, the majority of its reactions require in the presence of a catalytic
amount of Lewis acids,[26–28] such as Ru,[29] Yb,[20,30] Bi,[21] and Re[21] compounds
to generate activated monomeric species. Recently, Tohma et al. had found that
the activation of the iodosobenzene polymer ([PhIO]n) with inorganic bromide salts
in water is a powerful method for the effective oxidation of alcohols.[22] Secondary
alcohols were oxidized to ketones in excellent yields with the PhIO=KBr
system. Under the same conditions, primary alcohols and diols were oxidized to
the corresponding carboxylic acid or lactones, respectively. To develop a method
to selectively oxidize alcohols to aldehydes or ketones, we studied the oxidation of
4-nitrobenzyl alcohol with the PhIO=TEMPO=KBr system in water. Development
of aqueous-phase reactions is one of the active fields in organic synthesis because

CATALYTIC OXIDATION OF ALCOHOLS
2059
of demands for green chemical processes,[31,32] such as the oxidation of alcohols.[33,34]
When 4-nitrobenzyl alcohol was stirred in water with PhIO=TEMPO=KBr at room
temperature for 2 h, 94% conversion of the alcohol was observed. However, the
selectivity to aldehyde was low (48%), and only 43% of 4-nitrobenzaldehyde was
isolated (Table 1, entry 1). About one half of the alcohol was overoxidized to the
corresponding acid.
It is well known that in aqueous-phase reactions, addition of surfactants can
improve the reactions by solubilization[35,36] or micelle formation effects.[37–39] To
improve the selectivity of the oxidation of alcohols with the PhIO=TEMPO=KBr
system in water, we examined the effects using a variety of surfactants, including
anionic, cationic, and nonionic surfactants. Among those surfactants examined,
SDS, an anionic surfactant, and cetyltrimethyl ammonium bromide (CTAB), a
cationic surfactant, were found to be the most effective. In the presence of 20 mol%
of SDS, the oxidation of 4-nitrobenzyl alcohol in water completed in 2 h at room
temperature with 99% conversion of the reactant and about 95% isolated yield of
the corresponding 4-nitrobenzaldehyde (Table 1, entry 6). Tween-80 had only a
slightly beneficial effect on the oxidation (Table 1, entry 4). Tetrabutylammonium
bromide (TBAB) and triethylbenzylammonium chloride (TEBAC) had no beneficial
effect on the reaction, as most of the alcohol was overoxidized to the corresponding
acid (Table 1, entries 2 and 3). These results show a clear correlation between the
reaction selectivity and the hydrophile–lipophile balance (HLB) value of the surfac-
tants used.[40] The greater the HLB value of the surfactant used was, the greater reac-
tion selectivity was observed. To reach a reasonable selectivity, the HLB value of the
surfactant used should be greater than 15. For surfactants with similar HLB values,
ionic surfactants gave better results than nonionic surfactants. A surfactant with an
HLB value greater than 15 was often used as an emulsifier for the formation of oil in
water (O=W) emulsions or as a solubilization agent. During the experiment, we
observed that in the cases of CTAB, SDS, or Tween-80 as surfactant, the reaction
mixture was an emulsion all the time, but when TBAB or TEBAC was used as a
surfactant, the reaction proceeded in two stages. At the initial stage of the reaction,
the reaction mixture was an emulsion, and at the later stage, the reaction mixture
Table 1. Effect of surfactants on the oxidation of p-nitrobenzyl alcohola
Entry
Surfactant=HLBb
Conversion=selectivityc (%)
Yieldd (%)
1
—
94=48
99=37
91=31
80=79
99=90
99=95
43
30
28
65
87
95
2
TBAB=8.8
TEBAC=11.4
Tween-80=15
CTAB=15.8
SDS=40
3
4e
5
6
aReaction conditions: p-nitrobenzyl alcohol (1 mmol), PhIO (2.2 mmol), TEMPO
(0.1 mmol), KBr (0.2 mmol), surfactant (0.2 mmol), water (5 mL) at room temperature for 2 h.
bCalculated according to Davis law.
cGC conversion and selectivity.
dIsolated yield.
e0.1 g Tween-80 was added.

2060
C. ZHU, Y. WEI, AND L. JI
Figure 1. Effects of the amounts of TEMPO on the oxidation of 4-nitrobenzyl alcohol. Reaction
conditions: 4-nitrobenzyl alcohol (1 mmol), PhIO (2.2 mmol), KBr (0.2 mmol), surfactant (0.2 mmol),
TEMPO, and water (5 mL) at room temperature for 1 h.
gradually turned clean and solid was precipitated. It is believed that the selectivity of
the reaction decreases significantly at the later stage; that is, when the reactants,
especially TEMPO, could not disperse efficiently in the reaction mixture, the
system would actually become a PhIO=KBr system and lead to the formation of
4-nitrobenzoic acid.
To optimize the conditions of the oxidation, the dosages of TEMPO and PhIO
were studied using 1 mmol of 4-nitrobenzyl alcohol as substrate. The reaction pro-
ceeded without any problem, even with 1 mol% TEMPO, except it took a longer
reaction time. Addition of 10 mol% of TEMPO was enough to guarantee high con-
version and selectivity (Fig. 1).
Figure 2 shows that to guarantee high conversion and good aldehyde to acid
selectivity, less than 2.2 equivalents of PhIO should be used. Remarkable overoxida-
tion of aldehyde to acid occured when 2.5 equivalents of PhIO was used.
Figure 2. Effects of the amounts of PhIO on the oxidation of 4-nitrobenzyl alcohol. Reaction conditions:
4-nitrobenzyl alcohol (1 mmol), PhIO, KBr (0.2 mmol), surfactant (0.2 mmol), TEMPO (0.1 mmol), and
water (5 mL) at room temperature for 0.5 h.

CATALYTIC OXIDATION OF ALCOHOLS
2061
Oxidation of a Variety of Alcohols with PhIO/TEMPO/KBr/SDS
System
The scope of the present four-component oxidizing system PhIO=TEMPO=
KBr=SDS toward various kinds of alcohols, including benzylic, allylic, heterocyclic,
and aliphatic alcohols, was examined. Results are summarized in Table 2.
Table 2. PhIO=TEMPO=KBr=SDS-catalyzed oxidation of alcohols to aldehydes or ketonesa
Entry
1
Alcohols
Products
Time (h)
Conversionb (%)
Yieldc (%)
0.5
99
93
2
1
99
92
3
4
0.25
0.5
99
95
98
94
5d
2
1
7
91
95
90
85
90
84
6
7
8
4
6
80
79
72
64
9d
10d
11
8
6
65
94
48
78
n-C11H23-CH2OH
n-C11H23-CHO
12
8
90
75
aReaction conditions: alcohol (1 mmol), PhIO (2.2 mmol), TEMPO (0.1 mmol), KBr (0.2 mmol),
surfactant (0.2 mmol), and water(5 mL) at room temperature.
bGC conversion.
cYields of isolated products unless otherwise noted.
dYields were determined by GC.

2062
C. ZHU, Y. WEI, AND L. JI
Table 3. Competitive oxidation of primary and secondary alcoholsa
Entry
Substrate
Product
Time (h)
Yieldb (%)
95
þ
þ
1
2
0.5
4
<10
n-C11H23-CH2OH
þ
n-C11H23-CHO
þ
88
27
aThe reactions were carried out on a 1:1 mixture of primary and secondary alcohols, on a 1-mmol scale.
bIsolated yield.
Oxidation of alcohol in benzylic and allylic cases provides aldehyde or ketone
with high conversion and good yields (Table 2, entries 1–7). Electron-rich and
electron-deficient benzylic alcohols show no obvious difference. Even secondary
alcohols such as diphenylmethanol were selectively oxidized to ketones effectively
(Table 2, entry 7). The double bond of allylic alcohol was not oxidized (Table 2,
entry 6). For the oxidation of primary alcohols, no noticeable overoxidation of alde-
hyde to carboxylic acids was detected. Aliphatic and heterocyclic alcohols were less
reactive than benzylic and allylic alcohols toward this system. Aliphatic alcohols
were oxidized to the corresponding aldehydes or ketones in reasonable yields in
prolonged reaction times (Table 2, entries 8, 11, and 12). For the oxidation of
furan-2-yl methanol, a heterocyclic alcohol, less conversion, and less yield were
observed even with prolonged reaction time (Table 2, entry 10).
Table 3 shows the results of the competitive oxidation of primary and second-
ary alcohols. The competing oxidation of an equimolar mixture of benzyl alcohol
and 1-phenylethanol resulted in 95% yield of benzaldehyde and less than 10% yield
of acetophenone (Table 3, entry 1). Oxidation of an equimolar mixture of
dedocan-1-ol and octan-2-ol gave 88% dedocanal and 27% octan-2-one, respectively
(Table 3, entry 2). These results suggest that chemoselective oxidation of primary
alcoholic functionality in the presence of secondary alcoholic functionality is
possible with the present PhIO=TEMPO=KBr=SDS oxidation system in water.
Mechanistic Aspects
The catalytic system of PhIO=KBr for the oxidation of alcohols was first
developed by Tohma and coworkers.[22] Electrospray ionization–mass spectrometric
(ESI-MS) studies suggested that a highly reactive iodine species, C6H5I(Br)OꢀKþ(1),
is first formed in the reaction and then reacts with primary alcohols to yield the
corresponding carboxylic acids or with secondary alcohols to give ketones with
regeneration of KBr.[41]

CATALYTIC OXIDATION OF ALCOHOLS
2063
Scheme 2. Tentative mechanism for oxidation of alcohols with PhIO=TEMPO=KBr=SDS.
For the present PhIO=TEMPO=KBr=SDS catalytic oxidation system, both
primary and secondary alcohols give carbonyl compounds. TEMPO must play a
key role in this selectivity. As a result of these experimental observations and accord-
ing to Tohma’s preceding studies, we propose a possible reaction pathway
(Scheme 2). TEMPO would be the active oxidant in this reaction. Polymeric iodoso-
benzene ([PhIO]n) is initially depolymerized by KBr to form the highly reactive
intermediate 1, and the role of 1 is to regenerate TEMPO from TEMPOH.
CONCLUSION
In summary, an efficient, facile, and rapid oxidation of alcohols to the corres-
ponding aldehydes or ketones with the PhIO=TEMPO=KBr=SDS system has been
developed. (PhIO)n activated by a catalytic amount of KBr is a new reoxidant of
TEMPOH, which allowed the oxidation of primary and secondary alcohols in water
at room temperature to afford aldehydes or ketones in excellent yields and high sel-
ectivity without overoxidation to carboxylic acids. Selective oxidation of primary
alcohols in the presence of secondary alcohols was also achieved. Development of
immobilized and recyclable iodine(III) reagents is currently under investigation.
EXPERIMENTAL
All chemicals (analytical reagent grade) were obtained from commercial
resources and used without further purification. Gas chromatographic (GC) analysis
was performed on an Agilent GC-6820 chromatograph equipped with a
30 m ꢁ 0.32 mm ꢁ 0.5 mm HP-Innowax capillary column and a flame ionization
1
detector; H NMR spectra were obtained with tetramethylsilane (TMS) as internal
standard using a Bruker DRX 500 (500-MHz) spectrometer. Infrared (IR) spectra
were recorded on a Shimadzu spectrometer using KBr discs. Products were
all known compounds and were identified by comparing their physical and
spectroscopic data with those reported in the literature.
Typical Experimental Procedure for Oxidation of Alcohols
Alcohol (1 mmol), PhIO (2.2 mmol), TEMPO (0.1 mmol), KBr (0.2 mmol),
and SDS (0.2 mmol) were mixed with water (5 mL) and stirred at room temperature

2064
C. ZHU, Y. WEI, AND L. JI
for several hours. The reaction progress was checked by gas or thin-layer chromato-
graphy (TLC). After completion, the mixture was extracted with n-hexane (5ꢁ 5 mL)
and then filtered. The combined n-hexane phase was concentrated under vacuum,
and the crude product was purified by column chromatography (petroleum ether=ethyl
acetate ¼ 10=1) to provide the analytically pure aldehyde or ketone, which was
characterized by 1H NMR and IR analysis.
ACKNOWLEDGMENT
We are grateful to Nanjing University of Science and Technology for financial
support.
REFERENCES
´
1. Tojo, G.; Fernandez, M. Oxidation of Alcohols to Aldehydes and Ketones: A Guide to
Current Common Practice; Springer: New York, 2006.
2. Hudlicky´, M. Oxidations in Organic Chemistry; American Chemical Society: Washington,
DC, 1990.
3. Varvoglis, A. Hypervalent Iodine in Organic Chemistry; Academic Press: London, 1997.
4. Stang, P. J.; Zhdankin, V. V. Organic polyvalent iodine compounds. Chem. Rev. 1996,
96, 1123–1178.
5. Wirth, T.; Hirt, U. H. Hypervalent iodine compounds: Recent advances in synthetic
applications. Synthesis 1999, 1271–1287.
6. Moriarty, R. M.; Prakash, O. Oxidation of carbonyl compounds with organohypervalent
iodine reagents. Org. React. 1999, 54, 273–418.
7. Dess, D. B.; Martin, J. C. Readily accessible 12-I-5 oxidant for the conversion of primary
and secondary alcohols to aldehydes and ketones. J. Org. Chem. 1983, 48, 4155–4156.
8. Dess, D. B.; Martin, J. C. A useful 12-I-5 triacetoxyperiodinane (the Dess–Martin
periodinane) for the selective oxidation of primary or secondary alcohols and a variety
of related 12-I-5 species. J. Am. Chem. Soc. 1991, 113, 7277–7287.
9. Meyer, S. D.; Schreiber, S. L. Acceleration of the Dess–Martin oxidation by water. J. Org.
Chem. 1994, 59, 7549–7552.
10. Frigerio, M.; Santagostino, M. A mild oxidizing agent for alcohols and 1,2-diols:
o-Iodoxy-benzoic acid (IBX) in DMSO. Tetrahedron Lett. 1994, 35, 8019–8022.
11. Frigerio, M.; Santagostino, M.; Sputore, S.; Palmisano, G. Oxidation of alcohols with
o-iodoxybenzoic acid in DMSO: A new insight into an old hypervalent iodine reagent.
J. Org. Chem. 1995, 60, 7272–7276.
12. Corey, E. J.; Palani, A. A method for the selective oxidation of 1,4-diols to lactols.
Tetrahedron Lett. 1995, 36, 3485–3488.
13. Tsubokawa, N.; Kimoto, T.; Endo, T. Oxidation of alcohols with copper(II) salts
mediated by nitroxyl radicals immobilized on ultrafine silica and ferrite surface. J. Mol.
Catal. A Chem. 1995, 101, 45–50.
14. Sheldon, R. A.; Arends, I. Catalytic oxidations mediated by metal ions and nitroxyl
radicals. J. Mol. Catal. A: Chem. 2006, 251, 200–214.
15. Miyazawa, T.; Endo, T. Oxidation of diols with oxoaminium salts. J. Org. Chem. 1985,
50, 3930–3931.
16. Yamaguchi, M.; Miyazawa, T.; Takata, T.; Endo, T. Application of redox system based
on nitroxides to organic synthesis. Pure Appl. Chem. 1990, 62, 217–222.

CATALYTIC OXIDATION OF ALCOHOLS
2065
17. Sheldon, R. A.; Arends, I. W. C. E.; Ten Brink, G.-J.; Dijksman, A. Green, catalytic
oxidation of alcohols. Acc. Chem. Res. 2002, 35, 774–781.
18. Dijksman, A.; Arends, I. W. C. E.; Sheldon, R. A. A comparison of the activity of
polymer immobilised TEMPO (PIPO) with MCM-41 and silica-supported TEMPO as
heterogeneous catalysts for the oxidation of alcohols. Synlett 2001, 102–104.
19. De Mico, A.; Margarita, R.; Parlanti, L.; Vescovi, A.; Piancatelli, G. A versatile
and highly selective hypervalent iodine(III)=2,2,6,6-tetramethyl-1-piperidinyloxyl-
mediated oxidation of alcohols to carbonyl compounds. J. Org. Chem. 1997, 62,
6974–6977.
`
20. Vatele, J.-M. Yb(OTf)3-catalyzed oxidation of alcohols with iodosylbenzene mediated by
TEMPO. Synlett 2006, 2055–2058.
`
21. Vatele, J.-M. Lewis acid–promoted oxidative rearrangement of tertiary allylic alcohols
with the PhIO=TEMPO system. Synlett 2008, 1785–1788.
22. Tohma, H.; Takizawa, S.; Maegawa, T.; Kita, Y. Facile and clean oxidation of alcohols
in water using hypervalent iodine(III) reagents. Angew. Chem. Int. Ed. 2000, 39,
1306–1308.
23. Wei, Y.; Cai, M.; Lu, C. Studies on catalytic side-chain oxidation of nitroaromatics to
aldehydes with oxygen. Catal. Lett. 2003, 90, 81–84.
24. Liu, L.; Ma, J.; Wei, Y. Molecular sieve–promoted copper-catalyzed aerobic oxidation
of alcohols to corresponding aldehydes or ketones. J. Mol. Catal. A: Chem. 2008,
291, 1–4.
25. Liu, L.; Ji, L.; Wei, Y. Base-promoted aerobic oxidation of alcohols to corresponding
aldehydes or ketones catalyzed by CuCl=TEMPO. Catal. Commun. 2008, 9, 1379–1382.
26. Moriarty, R. M.; Penmasta, R.; Prakash, I. Possible role of Lewis acid catalysis in the
oxidation of alkenes and a,b-unsaturated ketones using bleomycin-Zn(II) and bleomycin-
Fe(III)-iodosylbenzene in aqueous methanol. Tetrahedron Lett. 1985, 26, 4699–4702.
27. Yang, Y.; Diederich, F.; Valentine, J. S. Lewis acidic catalysts for olefin epoxidation by
iodosylbenzene. J. Am. Chem. Soc. 1991, 113, 7195–7205.
28. Fukase, K.; Kinoshita, I.; Kanoh, T.; Nakai, Y.; Hasuoka, A.; Kusumoto, S. A novel
method for stereoselective glycosidation with thioglycosides: Promotion by hypervalent
iodine reagents prepared from PhIO and various acids. Tetrahedron 1996, 52, 3897–3904.
29. Muller, P.; Godoy, J. Catalyzed oxidation of alcohols and aldehydes with iodosylbenzene.
¨
Tetrahedron Lett. 1981, 22, 2361–2364.
30. Yokoo, T.; Matsumoto, K.; Oshima, K.; Utimoto, K. Ytterbium-catalyzed oxidation
of alcohols to aldehydes and ketones by means of iodosylbenzene. Chem. Lett. 1993,
571–572.
31. Cornils, B.; Herrmann, W. A. (Eds.). Aqueous-Phase Organometallic Catalysis; Wiley-
VCH: Weinheim, 1998.
32. Lindstrom, U. M. Stereoselective organic reactions in water. Chem. Rev. 2002, 102,
2751–2772.
33. Liu, Z.; Shang, X.; Chai, L. An atom-efficient catalytic oxidation of alcohols using
TEMPO=I2O5 in water. Catal. Lett. 2008, 123, 317–320.
34. Takenaga, N.; Goto, A.; Yoshimura, M.; Fujioka, H.; Dohi, T.; Kita, Y. Hypervalent
iodine(III)=Et4NþBrꢀ combination in water for green and racemization-free aqueous
oxidation of alcohols. Tetrahedron Lett. 2009, 50, 3227–3229.
35. Tascioglu, G. Micellar solutions as reaction media. Tetrahedron 1996, 52, 11113–11152.
36. Graciaa, A.; Lachaise, J.; Morel, G.; Salager, J. L.; Bourrel, M. Optimal Phase Behavior of
Water=Oil Blend=Surfactant Systems; Springer: Berlin, 2008.
37. Tohma, H.; Takizawa, S.; Watanabe, H.; Kita, Y. Hypervalent iodine(III) oxidation
catalyzed by quaternary ammonium salt in micellar systems. Tetrahedron Lett. 1998,
39, 4547–4550.

2066
C. ZHU, Y. WEI, AND L. JI
38. Mehta, S. K.; Chaudhary, S.; Kumar, R.; Bhasin, K. K. Facile solubilization of organo-
chalcogen compounds in mixed micelle formation of binary and ternary cationic–nonionic
surfactant mixtures. J. Phys. Chem. B 2009, 113, 7188–7193.
39. Tohma, H.; Takizawa, S.; Watanabe, H.; Fukuoka, Y.; Maegawa, T.; Kita, Y.
Hypervalent iodine(V)–induced asymmetric oxidation of sulfides to sulfoxides mediated
by reversed micelles: Novel nonmetallic catalytic system. J. Org. Chem. 1999, 64,
3519–3523.
40. Marszall, L.; Lin, I. J. Partition Coefficient, HLB, and Effective Chain Length of
Surface-Active Agents; Springer: Berlin, 2007.
41. Tohma, H.; Maegawa, T.; Takizawa, S.; Kita, Y. Facile and clean oxidation of
alcohols in water using hypervalent iodine(III) reagents. Adv. Synth. Catal. 2002, 344,
328–337.