M-iodosylbenzoic acid: Recyclable hypervalent iodine reagent for-tosyloxylation and-mesyloxylation of ketones

Article abstract of DOI:10.1080/00397910902838870

m-Iodosylbenzoic acid-mediated reactions of various carbonyl compounds provided-organosulfonyloxy carbonyl compounds in good yields. The final products could be easily isolated without any chromatographic purification by simple treatment of the crude mixt

Full text of DOI:10.1080/00397910902838870

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m-Iodosylbenzoic Acid:
Recyclable Hypervalent Iodine
Reagent for α-Tosyloxylation
and α-Mesyloxylation of
Ketones
Mekhman S. Yusubov a , Tatyana V. Funk a , Roza Y.
Yusubova a , Galina Zholobova a , Andreas Kirschning
b , Joo Yeon Park c & Ki-Whan Chi c
a Siberian State Medical University, Tomsk, Russiaand
Tomsk Polytechnic University, Tomsk, Russia
b Institut für Organische Chemie and Zentrum für
Biomolekulare Wirkstoffchemie (BMWZ), Leibniz
Universität Hannover, Hannover, Germany
c Department of Chemistry, University of Ulsan,
Ulsan, Republic of Korea
Published online: 07 Oct 2009.
To cite this article: Mekhman S. Yusubov , Tatyana V. Funk , Roza Y. Yusubova ,
Galina Zholobova , Andreas Kirschning , Joo Yeon Park & Ki-Whan Chi (2009) m-
Iodosylbenzoic Acid: Recyclable Hypervalent Iodine Reagent for α-Tosyloxylation and
α-Mesyloxylation of Ketones, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 39:21, 3772-3784, DOI:
10.1080/00397910902838870
To link to this article: http://dx.doi.org/10.1080/00397910902838870

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Synthetic Communications1, 39: 3772–3784, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902838870
m-Iodosylbenzoic Acid: Recyclable Hypervalent
Iodine Reagent for a-Tosyloxylation
and a-Mesyloxylation of Ketones
Mekhman S. Yusubov,1 Tatyana V. Funk,1 Roza Y. Yusubova,1
Galina Zholobova,1 Andreas Kirschning,2
Joo Yeon Park,3 and Ki-Whan Chi3
1Siberian State Medical University, Tomsk, Russia, and Tomsk
Polytechnic University, Tomsk, Russia
2Institut fur Organische Chemie and Zentrum fur Biomolekulare
¨
¨
Wirkstoffchemie (BMWZ), Leibniz Universita¨t Hannover,
Hannover, Germany
3Department of Chemistry, University of Ulsan, Ulsan,
Republic of Korea
Abstract: m-Iodosylbenzoic acid–mediated reactions of various carbonyl compounds
provided a-organosulfonyloxy carbonyl compounds in good yields. The final
products could be easily isolated without any chromatographic purification by
simple treatment of the crude mixture with an anionic exchange resin.
Keywords: Hypervalent
a-sulfonylation of ketones
iodine,
a-organosulfonyloxy
ketones,
recycle,
Received October 21, 2008.
Address correspondence to Mekhman S. Yusubov, Tomsk Polytechnis
University, Chemistry, 30 Lenin St., Tomsk 634050, Russian Federation. E-mail:
myusubov@yandex.ru; Andreas Kirschning, Institut fur Organische Chemie and
¨
Zentrum fur Biomolekulare Wirkstoffchemie (BMWZ), Leibniz Universita¨t
¨
Hannover, Schneiderberg 1B, Hannover D-30167, Germany. E-mail: andreas.
kirschning@oci.uni-hannover.de; and Ki-Whan Chi, Department of Chemistry,
University of Ulsan, 680-749 Ulsan, Republic of Korea. E-mail: kwchi@ulsan.
ac.kr
3772

m-Iodosylbenzoic Acid
3773
a-Organosulfonyloxy ketones are useful building blocks for the construction
of heterocyclic compounds such as thiazoles, selenazoles, oxazoles, imida-
zoles, pyrazoles, benzofurans, and lactones.[1] Since the early 1980s, hyper-
valent iodine compounds have attracted significant interest as mild and
selective oxidizing reagents in synthetic organic chemistry.[2] Among them,
[hydroxy(mesyloxy)iodo]benzene (HMIB) and its tosyloxy analog (HTIB)
are useful reagents for a-mesyloxylation and a-tosyloxylation of
ketones.[1g,3] Common by-products in the reactions of HMIB and HTIB
are their corresponding reduced products, namely aryliodides, which often
have to be removed by a chromatographic treatment. A tedious chromato-
graphic purification is also needed for the reaction with iodine(III) oxidant if
the oxidant is employed in excess or not fully consumed.
Togo and coworkers have studied the a-tosyloxylation of ketones
using five novel [hydroxy(tosyloxy)iodo]arenes that bear 2-thienyl, 3-thie-
nyl, N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifluoro-
methy)phenyl as arenes.[4] Commonly, a-tosyloxylation of ketones was
achieved by the in situ formation of the active reagent by mixing (diace-
toxyiodo)arene (1.0–1.2 eq.) and p-toluenesulfonic acid monohydrate
(2.0–2.4 eq.). Conventional workup of extraction and chromatographic
purification was required in this synthetic method. Also, iodosylbenzene
can serve as an iodine(III) reagent for a-tosyloxylations.[5] Additionally,
poly[4-hydroxy(tosyloxy)iodo]styrene and poly{R-methyl[4-hydroxy
(tosyloxy)iodo]styrene} can serve as iodine(III) reagents,[6] which lead
to simplified workup, although the a-sulfonyloxy ketones were purified
by flash chromatography.
Alternatively, homogeneously supported version of Koser’s salt
based on room-temperature ionic liquids were introduced by Handy and
Okello.[7] Isolation of a-tosyloxy ketones is achieved by simple extraction
with dichloromethane (DCM) and chromatographic purification on silica
gel. Tohma and coworkers[8] found that the monomeric recyclable hyper-
valent iodine(III) reagents 1,3,5,7-tetrakis[4-(diacetoxyiodo)phenyl]-
adamantine and tetrakis[4-(diacetoxyiodo)phenyl]methane can also be
employed for the synthesis of a-sulfonyloxy ketones. However, both of
these reagents require multistep procedures for their preparation.
In this report, we disclose a very simple method for the a-tosyloxyla-
tion and a-mesyloxylation of ketones with minimum purification that is
based on the tagged iodine(III) reagent, m-iodosylbenzoic acid (1).
Indeed, tagging strategies for reagents and catalysts have been widely
investigated, as they allow easy purification by means of specific phase
separation or scavenging.[9] m-Iodosylbenzoic acid (1) is an example of
a tagged iodine(III) reagent.[10] If it is treated in excess, unreacted reagent
can be conveniently removed at the end of the reaction by filtration after
treatment with anion exchange resin Amberlite IRA-900 (carbonate

3774
M. S. Yusubov et al.
Scheme 1. a-Organosulfonyloxylation of ketones with m-iodosobenzoic acid (1).
form) (Scheme 1). This concept can also be applied to scavenge a reduced
product such as m-iodobenzoic acid (2). Importantly, by-product 2,
which also serves as the starting material for the preparation of 1, can
be easily regenerated (>95%) in a pure form from the polymeric salts 3
by treatment with aqueous HCl.
m-Iodosylbenzoic acid (1, 0.24 mmol) was added to a mixture of
ketones 4a–l (0.2 mmol) and p-toluenesulfonic acid monohydrate (or
methanesulfonic acid) (0.3–0.4 mmol) in CH3CN (1.0 mL). The reaction
mixture was stirred under the reaction conditions indicated in Table 1,
and the reactions were monitored by thin-layer chromatography
(TLC). Then, DCM (1.0 mL) was added, and the resulting solution was
cooled to 5ꢀC. Amberlite IRA-900 (900–1200 mg; carbonate form) was
added, and the mixture was stirred for 5 min. The polymer was removed
by filtration, and the solution was concentrated at reduced pressure to
afford pure a-organosulfonyloxy ketones 5 or 6 as judged by NMR
spectroscopy in 51–93% yield. m-Iodobenzoic acid (2) can easily be
regenerated from the produced salts 3 by treatment with aqueous HCl
and oxidation with Ac2O=H2O2 to yield 1 without additional purification
as described previously.[10]
Various forms of Amberlite IRA-900 (azide, carbonate, and
hydroxide forms) were tested for the removal of unreacted m-iodosoben-
zoic acid (1) and reduced m-iodobenzoic acid (2). The acids 1 and 2 were
successfully removed only with the carbonate form of Amberlite IRA-
900. When Amberlite IRA-900 in a hydroxide form was used, hydrolysis
and elimination reactions were accompanied instead. In addition,

m-Iodosylbenzoic Acid
3775
Table 1. a-Organosulfonyloxylation of ketones, diketones, and a b-ketoester
Temp. Time Yielda
Entry
1
Ketone 4
Products 5, 6
(ꢀC)
(h)
(%)
60
1.0
67
53
Reflux 1.0
Reflux 2.0
2
70
3
Reflux 2.0
75
RT
RT
8
1.5
51
54
4
5
Reflux 3.0
Reflux 2.0
96
84
(Continued )

3776
M. S. Yusubov et al.
Table 1. Continued
Temp. Time Yielda
Entry
6
Ketone 4
Products 5, 6
(ꢀC)
(h)
(%)
60
6.0
81
Reflux 5.0
Reflux 13
88
84
7
8
9
Reflux 2.0
77
RT
RT
1.0
1.0
87
79
10
11
RT
1.0
88
RT
RT
1.0
1.0
93
92
12
RT
4.0
87
aIsolated yields of pure products.
a-azidoketones 7 (Scheme 2) were obtained, especially at reflux tempera-
ture, when Amberlite IRA-900 in an azide anionic form was used.
a-Tosyloxylation of 3-acetylpyridine (4 m) was tried in vain. In the
case of a-tetralone (4n), the reaction mixture darkened and the formation

m-Iodosylbenzoic Acid
3777
Scheme 2. Synthesis of a-azidoketones.
of complex by-products was observed. With ketones 4o–q, the reaction
proceeded successfully, but the products had a strong tendency to stick to
the resin Amberlite IRA-900 (Figure 1).
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker DRX spectrometer (200 or
500 MHz); CDCl3 was used as a solvent, and tetramethylsilane (TMS)
was used as an internal standard. Infrared (IR) spectra were measured
with a Perkin-Elmer Spectrum RX FTIR system. Thin-layer chromato-
graphy (TLC) was performed on precoated silica-gel 60 F254 plates
(0.25 mm thick, Merck). Melting points were determined with a Kofler
apparatus and are uncorrected. Commercially available solvents and
reagents (Fluka, Aldrich, Merck) were used without further purification.
m-Iodosylbenzoic acid (2) was prepared according to the published litera-
ture.[8] Amberlite IRA-900 (chloride form) was obtained from Supelco.
General Procedure for a-Organosulfonyloxylation of b-Diketones
m-Iodosylbenzoic acid (1, 0.24 mmol) was added to a mixture of
b-diketones (0.2 mmol) and p-toluenesulfonic acid monohydrate (or
methanesulfonic acid) (0.3–0.4 mmol) in CH3CN (1.0 mL). The reaction
Figure 1. Structures of ketones 4o–q.

3778
M. S. Yusubov et al.
mixture was stirred at room temperature for 1.0–4.0 h, and the reaction
was monitored by TLC. Then dichloromethane (1.0 mL) was added,
and the resulting solution was cooled to 0ꢀC. Amberlite IRA-900 (900–
1200 mg, carbonate form) was added, and the mixture was stirred for
5 min. The polymeric solids were removed by filtration, and the filtrate
was concentrated at reduced pressure to afford pure a-organosulfonyloxy
1
ketones as judged by the H NMR spectra.
Data
1-Tosyloxyacetone (Toluene-4-sulfonic acid 2-oxopropyl Ester) (5a)
1
Mp 34–35ꢀC (lit.[3a] mp 35ꢀC). H NMR (CDCl3, 200 MHz) d ¼ 2.21 (s,
3H, CH3–CO), 2.46 (s, 3H, CH3), 4.48 (s, 2H, CH2), 7.39 (d, J ¼ 8.0 Hz,
Hz, 2Harom.), 7.79 (d, J ¼ 8.0 Hz, 2Harom.).
1-Mesyloxyacetone (Methanesulfonic Acid 2-Oxopropyl Ester) (6a)
1
Light yellow oil (lit.[3b] light yellow oil). H NMR (CDCl3, 500 MHz)
d ¼ 2.22 (s, 3H, CH3–CO), 3.19 (s, 3H, CH3), 4.78 (s, 2H, CH2).
1-Tosyloxypentan-2-one (5b) and 3-Tosyloxypentan-2-one (5b0) (1:2.5)
1
Oil. 1-Tosyloxypentan-2-one (5b): H NMR (CDCl3, 500 MHz) d ¼ 0.81
(t, 3H, CH3), 1.58 (m, 2H, CH2), 2.46 (s, 3H, CH3), 2.47 (t, 2H, CH2),
4.48 (s, 2H, CH2), 7.35 (d, J ¼ 8.0 Hz, 2Harom.), 7.79 (d, J ¼ 8.0 Hz,
2Harom.). 3-Tosyloxypentan-2-one (5b0): 1H NMR (CDCl3, 500 MHz)
d ¼ 0.81 (t, 3H, CH3), 1.73 (m, 2H, CH2), 2.19 (s, 3H, CH3–CO), 2.46
(s, 3H, CH3), 4.56 (dd, J ¼ 7.5, 5.5 Hz, 1H, CH), 7.37 (d, J ¼ 8.0 Hz,
2Harom.), 7.81 (d, J ¼ 8.0 Hz, 2Harom.).
1-Tosyloxyhexan-2-one (5c) and 3-Tosyloxyhexan-2-one (5c0) (1:2)
1
Oil. 1-Tosyloxyhexan-2-one (5c): H NMR (CDCl3, 500 MHz) d ¼ 0.72
(t, 3H, CH3), 1.16 (m, 2H, CH2), 1.55 (m, 2H, CH2), 2.42 (s, 3H,
CH3), 2.46 (t, 2H, CH2), 4.56 (dd, J ¼ 8.4, 4.8 Hz, 1H, CH), 7.35 (d,
J ¼ 8.0 Hz, 2Harom.), 7.79 (d, J ¼ 8.0 Hz, 2Harom.). 3-Tosyloxyhexan-2-
1
one (5c0): H NMR (CDCl3, 500 MHz) d ¼ 0.90 (t, 3H, CH3), 1.31 (m,
2H, CH2), 1.82 (m, 2H, CH2), 2.15 (s, 3H, CH3-CO), 2.42 (s, 3H,
CH3), 4.56 (dd, J ¼ 8.4, 4.8 Hz, 1H, CH), 7.37 (d, J ¼ 8.0 Hz, 2Harom.),
7.81 (d, J ¼ 8.0 Hz, 2Harom.).

m-Iodosylbenzoic Acid
3779
2-Tosyloxycyclohexanone (Toluene-4-sulfonic Acid 2-Oxocyclohexyl
Ester) (5d)
Mp 73–74ꢀC (lit.[3a] mp 74–76ꢀC). 1H NMR (CDCl3, 200 MHz) d ¼ 1.69–
2.00 (m, 5H), 2.48 (s, 3H, CH3), 2.28–2.58 (m, 3H), 4.90 (dd, J ¼ 9.8,
5.9 Hz, 1H, CH), 7.35 (d, J ¼ 8.0 Hz, 2Harom.), 7.86 (d, J ¼ 8.0 Hz, 2Harom.).
2-Mesyloxycyclohexanone (Methanesulfonic Acid 2-Oxocyclohexyl
Ester) (6d)
Mp 57ꢀC (lit.[3b] mp 58–59ꢀC). 1H NMR (CDCl3, 500 MHz) d ¼ 1.61 (m,
1H), 1.76 (m, 1H), 1.90 (m, 1H), 2.00 (m, 1H), 2.03 (m, 1H), 2.15 (m, 1H),
2.41 (m, 1H), 2.57 (m, 1H), 3.21 (s, 3H, CH3), 5.08 (dd, J ¼ 11.5, 6.0 Hz,
1H, CH).
Tosyloxyacetophenone (Toluene-4-sulfonic Acid 2-Oxo-2-phenylethyl
Ester) (5e)
1
Mp 92ꢀC (lit.[3a] mp 91–92ꢀC). H NMR (CDCl3, 200 MHz) d ¼ 2.44 (s,
3H, CH3), 5.26 (s, 2H, CH2), 7.35 (d, J ¼ 8.4 Hz, 2Harom.), 7.46 (t,
J ¼ 8.1 Hz, 2Harom.), 7.57 (t, J ¼ 8.1 Hz, 1Harom.), 7.83–7.86 (m, 4Harom.).
Mesyloxyacetophenone (Methanesulfonic Acid 2-Oxo-2-phenylethyl
Ester) (6e)
1
Mp 75–77ꢀC (lit.[3b] mp 76–77ꢀC). H NMR (CDCl3, 500 MHz) d ¼3.29
(s, 3H, CH3), 5.52 (s, 2H, CH2), 7.53 (t, J ¼ 8.5 Hz, 2Harom.), 7.66 (t,
J ¼ 8.5 Hz, 1Harom.), 7.88 (d, J ¼ 8.5 Hz, 2Harom.).
(Tosyloxy)methyl 2-Furanyl Ketone (Toluene-4-sulfonic Acid
2-Furan-2-yl-2-oxo-ethyl Ester) (5f)
1
Mp 64–66ꢀC (lit.[1a] mp 63–64ꢀC). H NMR (CDCl3, 200 MHz) d ¼ 2.45
(s, 3H, CH3), 5.08 (s, 2H, CH2), 6.58 (dd, J ¼ 3.7, 1.7 Hz, 1Harom.), 7.34
(dd, J ¼ 3.7, 0.7 Hz, 1Harom.), 7.37 (d, J ¼ 8.2 Hz, 2Harom.), 7.60 (dd,
J ¼ 1.7, 0.7 Hz, 1Harom.), 7.86 (d, J ¼ 8.2 Hz, 2Harom.).
(Tosyloxy)methyl 2-Thienyl Ketone (5g)
1
Mp 90–92ꢀC (lit.[3a] mp 93–95ꢀC). H NMR (CDCl3, 500 MHz) d ¼ 2.36
(s, 3H, CH3), 5.00 (s, 2H, CH2), 7.07 (dd, J ¼ 5.0, 3.6 Hz, 1Harom.), 7.26

3780
M. S. Yusubov et al.
(d, J ¼ 8.0 Hz, 2Harom.), 7.65 (dd, J ¼ 5.0, 1.0 Hz, 1Harom.), 7.73 (dd,
J ¼ 3.6, 1.0 Hz, 1Harom.), 7.77 (d, J ¼ 8.1 Hz, 2Harom.).
(Mesyloxy)methyl 2-Thienyl Ketone (6g)
1
Mp 85–86ꢀC (lit.[3b] mp 87–88ꢀC). H NMR (CDCl3, 500 MHz) d ¼3.28
(s, 3H, CH3), 5.38 (s, 2H, CH2), 7.20 (dd, J ¼ 5.0, 3.6 Hz, 1Harom.), 7.26
(dd, J ¼ 5.0, 1.0 Hz, 1Harom.), 7.76 (dd, J ¼ 3.6, 1.0 Hz, 1Harom.).
2-Tosyloxyindan-1-one (5h)
Mp 110–112ꢀC (lit.[11] mp 113–114ꢀC). 1H NMR (CDCl3, 500 MHz)
d ¼ 2.46 (s, 3H, CH3), 3.26 (dd, J ¼ 17.0, 4.5 Hz, 1H), 3.65 (dd,
J ¼ 17.5, 8.0 Hz, 1H), 5.12 (dd, J ¼ 8.0, 5.0 Hz, 1H), 7.41 (m, 4Harom.),
7.63 (t, J ¼ 7.5 Hz, 1Harom.), 7.72 (d, J ¼ 7.5 Hz, 1Harom.), 7.93 (d,
J ¼ 8.0 Hz, 2Harom.).
a-Tosyloxy-2,4-pentadione (5i)
Mainly enol tautomer; mp 81ꢀC (lit.[3a] mp 82–83ꢀC). 1H NMR (500 MHz,
CDCl3) d ¼ 1.95 (s, 6H, CH3), 2.21 (s, 6H, CH3, keto form), 2.46 (s, 3H,
CH3, keto form), 2.48 (s, 3H, CH3), 5.20 (s, 1H, CH, keto form), 7.38
(d, J ¼ 8.19 Hz, 2Harom.), 7.80 (d, J ¼ 8.19 Hz, 2Harom.), 14.78 (s, 1H, OH).
a-Mesyloxy-2,4-pentadione (6i)
1
A mixture of keto-enol tautomers, colorless oil (lit.[3b] colorless oil). H
NMR (CDCl3, 500 MHz) d ¼ 2.21 (s, 6H, CH3), 2.29 (s, 6H, CH3), 3.15
(s, 3H, CH3), 3.17 (s, 3H, CH3), 5.46 (s, 1H, CH–OMs), 14.78 (s, 1H, OH).
a-Mesyloxy-1-phenyl-2,4-pentadione (6j)
1
Colorless oil (lit.[3c] oil). H NMR (CDCl3, 500 MHz) d ¼ 2.01 (s, 3H,
CH3), 3.23 (s, 3H, CH3), 6.23 (s, 1H, CH–OMs), 7.54 (t, J ¼ 7.5 Hz,
2Harom.), 7.80 (t, J ¼ 7.5 Hz, 1Harom.), 8.01 (d, J ¼ 7.5 Hz, 2Harom.).
Dibenzoyl(tosyloxy)methane (5k)
1
Mp 88–89ꢀC (lit.[3a] mp 88–90ꢀC). H NMR (CDCl3, 500 MHz) d ¼ 2.39
(s, 3H, CH3), 6.66 (s, 1H, CH–OTs), 7.17 (d, J ¼ 8.1 Hz, 2Harom.), 7.45 (t,

m-Iodosylbenzoic Acid
3781
J ¼ 7.5 Hz, 4Harom.), 7.56 (t, J ¼ 7.5 Hz, 2Harom.), 7.71 (d, J ¼ 8.1 Hz,
2Harom.), 7.96 (d, J ¼ 7.5 Hz, 4Harom.).
Dibenzoyl(mesyloxy)methane (6k)
Mp 152–154ꢀC (lit.[3b] mp 153–154ꢀC). 1H NMR (CDCl3, 500 MHz)
d ¼3.34 (s, 3H, CH3), 6.35 (s, 1H, CH–OMs), 7.53 (t, J ¼ 8.0 Hz,
4Harom.), 7.66 (t, J ¼ 8.0 Hz, 2Harom.), 7.90 (d, J ¼ 8.0 Hz, 4Harom.).
Ethyl(mesyloxy)acetoacetate (6l)
A mixture of keto-enol tautomers (4.5:1), colorless oil (lit.[3b] nearly col-
1
orless oil). H NMR (CDCl3, 500 MHz) d ¼ 1.34 (t, 3H, CH3), 2.18 (s,
3H, CH3, minor isomer), 2.37 (s, 3H, CH3), 3.19 (s, 3H, CH3, minor iso-
mer), 3.24 (s, 3H, CH3), 4.33 (q, 2H, CH2), 5.43 (s, 1H, CH–OMs). 2.00
(s, 3H, CH3). 3.23 (s, 3H, CH3). 6.23 (s, 1H, CH–OMs).
2-Azido-1-phenylethanone (7)
m-Iodosylbenzoic acid (1, 0.24 mmol) was added to a mixture of acetophe-
none (4e, 0.2 mmol) and p-toluenesulfonic acid monohydrate (or methane-
sulfonic acid) (0.3–0.4 mmol) in CH3CN (1.0 mL). The reaction mixture
was stirred at reflux for 3.0 h, and the reaction was monitored by TLC.
Then DCM (1.0 mL) was added, and the resulting solution was cooled
to 0ꢀC. Amberlite IRA-900 (800 mg, carbonate form) and Amberlite
IRA-900 (300 mg, azide form) were added, and the mixture was stirred
for 5 h at room temperature. The polymeric solids were removed by filtra-
tion, and the filtrate was concentrated at reduced pressure to afford pure
2-azido-1-phenylethanone (7) as a pale yellow oil (20 mg, 61%). 1H NMR
(CDCl3, 500 MHz) d ¼ 4.44 (s, 2H, CH2), 7.53 (t, J ¼ 8.5 Hz, 2Harom.),
7.66 (t, J ¼ 8.5 Hz, 1Harom.), 7.88 (d, J ¼ 8.5 Hz, 2Harom.).
CONCLUSION
In conclusion, we report here that the rarely employed m-iodosylbenzoic
acid is an ideally tagged iodine(III) reagent that allows the easiest purifi-
cation protocol for hypervalent aryliodine reagents known thus far. This
tagging concept was utilized in the mild a-organosulfonyloxylation of
ketones but should also be applicable for most other iodine(III)-mediated
reactions.

3782
M. S. Yusubov et al.
ACKNOWLEDGMENTS
M. S. Y. and A. K. thank Fonds der Chemischen Industrie for support of
this work. K. W. C., M. S. Y., and R. Y. Y. are grateful for the support
of the Brain Korea 21 program.
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benzene with trimethylsilyl enol ethers: A new general method for a-sulfony-
loxylation of carbonyl compounds. J. Org. Chem. 1989, 54 (5), 1101–1104; (b)
Moriarty, R. M.; Vaid, R. K.; Hopkins, T. E.; Vaid, B. K.; Prakash, O.
Hypervalent iodine oxidation of 5-keto acids and 4,6-diketo acids with
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