Solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one from Dess-Martin periodinane and its synthetic utility for α-tosyloxylation of ketones

Article abstract of DOI:10.1016/j.tetlet.2008.03.119

The solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one is reported from Dess-Martin periodinane and p-toluenesulfonic acid monohydrate using a grinding technique and is subsequently utilized for the α-tosyloxylation of a range of enolisable ketones.

Full text of DOI:10.1016/j.tetlet.2008.03.119

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Tetrahedron Letters 49 (2008) 3441–3443
Solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-
3(1H)-one from Dess–Martin periodinane and its synthetic utility
for a-tosyloxylation of ketones
Nandkishor N. Karade *, Girdharilal B. Tiwari, Sandeep V. Shinde,
Sumeet V. Gampawar, Jeevan M. Kondre
School of Chemical Sciences, Swami Ramanand Teerth Marathwada University, Nanded 431 606, Maharashtra, India
Received 5 February 2008; revised 15 March 2008; accepted 21 March 2008
Available online 28 March 2008
Abstract
The solvent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one is reported from Dess–Martin periodinane and
p-toluenesulfonic acid monohydrate using a grinding technique and is subsequently utilized for the a-tosyloxylation of a range of
enolisable ketones.
Ó 2008 Elsevier Ltd. All rights reserved.
Keywords: Hypervalent iodine; Dess–Martin periodinane; a-Tosyloxylation; PTSA; Solvent-free reactions
Recent decades have witnessed an exponential growth in
the applications of hypervalent iodine reagents in organic
synthesis.1 2-Iodoxybenzoic acid (IBX) 1 represents one
such versatile five-membered hypervalent iodine(V) hetero-
cycle derived from benziodoxole.2 It has been widely used
for various useful oxidative transformations.3 In 1983,
Dess and Martin carried out the reaction of IBX with
acetic anhydride at 100 °C for the preparation of tri-
acetoxybenziodoxole 2.4 In the following years, triacetate
2 has emerged as a chemoselective reagent of choice for
the oxidation of alcohols and in the present literature is
commonly referred to as Dess–Martin periodinane
(DMP).5 In contrast to IBX 1 and DMP 2, the analogous
five-membered trivalent iodine heterocycles derived from
benziodoxoles have received much less attention. However,
the significant contribution of Viktor Zhdankin has led to
the development of various trivalent iodine five-membered
heterocycles (Fig. 1), such as 1-hydroxy-1,2-benziodoxol-
3(1H)-one 3, 1-organosulfonoloxy-1,2-benziodoxol-3(1H)-
OAc
z
I
O
AcO
OH
O
OAc
I
I
O
O
O
O
O
3, Z = OH
4, Z = OSO2R
5, Z = CN
6, Z = NHCOR
7, Z = N3
1
IBX
2
DMP
8, Z = OTs
Fig. 1. Benziodoxole-based hypervalent iodine reagents.
one 4, 1-cyano-1,2-benziodoxol-3(1H)-one 5, 1-amido-1,2-
benziodoxol-3(1H)-one 6 and 1-azido-1,2-benziodoxol-
3(1H)-one 7.6 The distinctive feature of these heterocyclic
iodanes is their considerable higher stability than their acy-
clic analogs. These various benziodoxole derivatives have
found practical application as reagents for the oxidative
functionalization of organic substrates.7
*
The first preparation of 1-(p-toluenesulfonyloxy)-1,2-
benziodoxol-3(1H)-one 8 was reported by Zhdankin et al.
Corresponding author. Tel.: +91 2462 266999; fax: +91 2462 29245.
E-mail address: nnkarade2007@rediffmail.com (N. N. Karade).
0040-4039/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2008.03.119

3442
N. N. Karade et al. / Tetrahedron Letters 49 (2008) 3441–3443
Table 1
OTs
OAc
AcO
a-Tosyloxylation of enolisable ketones using 1-(p-toluenesulfonyloxy)-1,2-
benziodoxol-3(1H)-one in CH3CN
OAc
I
I
solvent-free
93%
p-TsOH.H2O
O
O
+
OTs
O
O
O
I
O
8
CH3CN
reflux
2
R2
R2
+
O
R1
R1
Scheme 1.
OTs
9 a-l
Reaction time (h) Yielda (%)
O
8
1
by the reaction of 1-hydroxy-1,2-benziodoxol-3(1H)-one 3
with p-toluenesulfonic acid monohydrate in the presence
of acetic anhydride.8 Another noteworthy solvent-free syn-
thesis of 8 involves the grinding of (diacetoxyiodo)benzene,
2-iodobenzoic acid and p-toluenesulfonic acid monohy-
drate in an agate mortar.9 In 1987, Toda et al. showed that
many reactions (but not all) can be conducted in high yields
under solvent-free conditions just by grinding the reactants
together.10 Usually these reactions were carried out on a
very small scale in an agate pestle and mortar. We decided
to extend this strategy for the reaction between Dess–
Martin periodinane and p-toluenesulfonic acid mono-
hydrate (Scheme 1). In a typical experimental procedure,
a homogeneous mixture of Dess–Martin periodinane
(2 mmol) and p-toluenesulfonic acid monohydrate
(2 mmol) was gently ground for 15 min using a pestle and
mortar. The formation of acetic acid, and wetting of the
reaction mixture was observed. The resulting reaction
mixture was washed with diethyl ether to remove liberated
acetic acid and dried under high vacuum to afford
1-(p-toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one 8 in
93% yield. The structure of this reagent 8 was established
from NMR and mass spectral analysis, and found perfectly
in agreement with that reported in the literature.11
Entry Product 9
a
b
c
d
e
f
C6H5COCH2OTs
1
1
1
88
63
76
69
88
67
79
73
67
69
71
74
4-CH3C6H4COCH2OTs
4-CH3OC6H4COCH2OTs
2,4-(CH3O)2C6H3COCH2OTs 1.5
4-BrC6H4COCH2OTs
2-BrC6H4COCH2OTs
2-ClC6H4COCH2OTs
4-NO2C6H4COCH2OTs
C6H5COCH(CH3)OTs
a-Tosyloxycyclohexanone
CH3COCH(OTs)COCH3
CH3COCH(OTs)COOCH3
1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
g
h
i
j
k
l
a
Isolated yields after chromatography.
alkynes.13 The synthetic application of 1-(p-toluenesulf-
onyloxy)-1,2-benziodoxol-3(1H)-one 8 is hitherto unknown
for the a-tosyloxylation of ketones. Herein, we have inves-
tigated the ability of 8 for the a-tosyloxylation reaction of
enolisable ketones and the results are summarized in Table
1.14 The method is quite general for the a-tosyloxylation of
enolisable ketones and in all the cases good to excellent
yields of the products were obtained. Alicyclic ketones such
as substituted acetophenones, propiophenone and cyclic
ketone such as cyclohexanone underwent the a-tosyloxyl-
ation reaction smoothly to afford the corresponding
products in reasonable yields. The methodology was also
extended to a-tosyloxylation of 1,3-dicarbonyl compounds
such as methyl acetoacetate and acetyl acetone to form the
respective a-tosyloxy products.
a-Tosyloxylation of ketones is most frequently achieved
using [hydroxy(tosyloxy)iodo]benzene, which is commonly
known as Kosser’s reagent.12 The utility of 1-(p-toluene-
sulfonyloxy)-1,2-benziodoxol-3(1H)-one 8 was previously
demonstrated for the oxidative nuclear iodination of aro-
matic rings as well as for the iodotosyloxylation of
TsO
OH
O
H
I
O
+
O
O
+
R1
I
O
R1
TsO
R1
R2
R2
O
R2
O
COOH
I
O
OTs
+
I
+
R1
COOH
TsO
R1
R2
R2
10
Scheme 2.

N. N. Karade et al. / Tetrahedron Letters 49 (2008) 3441–3443
3443
4. (a) Dess, D. E.; Martin, J. C. J. Org. Chem. 1983, 48, 4155; (b) Dess,
D. E.; Wilson, S. R.; Martin, J. C. J. Am. Chem. Soc. 1993, 115, 2488.
5. (a) Wipf, P.; Jung, J.-K. J. Org. Chem. 1998, 63, 3530; (b) Clive, D. L.;
Hisaindee, S. Chem. Commun. 1999, 2251; (c) Tueckmantel, W.;
Kozikowski, A. P.; Romanczyk, L. J. Am. Chem. Soc. 1999, 121,
12073; (d) Jeong, J. U.; Guo, C.; Fuchs, P. L. J. Am. Chem. Soc. 1999,
121, 2071.
6. (a) Zhdankin, V. V. Curr. Org. Synth. 2005, 2, 121; (b) Zhdankin, V.
V.; Ladziata, U. ARKIVOC 2005, ix, 26; (c) Zhdankin, V. V.; Kuehl,
C. J.; Krasutsky, A. P.; Bolz, J. T.; Simonsen, A. J. J. Org. Chem.
1996, 61, 6547.
7. (a) Ochiai, M.; Nakanishi, A.; Suefuji, T. Org. Lett. 2000, 2, 2923; (b)
Zhdankin, V. V.; Kuehl, C. J.; Krasutsky, A. P.; Bolz, J. T.; Mismash,
B.; Woodward, J. K.; Simonsen, A. J. Tetrahedron Lett. 1995, 36,
7975.
8. Zhdankin, V. V.; Kuehl, C. J.; Bolz, J. T.; Formaneck, M. S.;
Simonsen, A. J. Tetrahedron Lett. 1994, 35, 7323.
A tentative mechanism for the a-tosyloxylation of
ketones is shown in Scheme 2. The enol tautomer of the
ketone reacts with the electrophilic 1-(p-toluenesulfonyl-
oxy)-1,2-benziodoxol-3(1H)-one via ligand exchange to
form intermediate 10, which undergoes reductive elimina-
tion of 2-iodobenzoic acid to form the a-tosyloxy ketone.
In conclusion, we have demonstrated an efficient sol-
vent-free synthesis of 1-(p-toluenesulfonyloxy)-1,2-benzio-
doxol-3(1H)-one from the readily available Dess–Martin
periodinane and p-toluenesulfonic acid monohydrate. The
a-tosyloxylation of a range of ketones was successfully
carried out with 1-(p-toluenesulfonyloxy)-1,2-benziodoxol-
3(1H)-one in good to excellent yields. The development
of other synthetic applications of 1-(p-toluenesulfonyl-
oxy)-1,2-benziodoxol-3(1H)-one is underway.
9. Wirth, T.; Yusubov, M. Org. Lett. 2005, 3, 519.
10. (a) Toda, F.; Tanaka, K.; Sekikawa, A. J. Chem. Soc., Chem.
Commun. 1987, 279; (b) Toda, F.; Suzuki, T.; Higa, S. J. Chem. Soc.,
Perkin Trans. 1 1998, 3521; (c) Scott, J. L.; Raston, C. L. Green Chem.
2000, 2, 245.
Acknowledgement
The authors are thankful to the Department of Science
and Technology, New Delhi, India, for the financial
support (No. SR/FTP/CS-77/2005).
11. Experimental procedure for the preparation of 1-(p-toluenesulfonyl-
oxy)-1,2- benziodoxol-3(1H)-one: A homogeneous mixture of Dess–
Martin periodinane (2 mmol) and p-toluenesulfonic acid mono-
hydrate (2.1 mmol) was gently ground for 15 min using a pestle and
mortar. The liberation of acetic acid and wetting of the reaction
mixture was observed. After completion of the reaction, the solid
residue was washed with diethyl ether (5 mL) and concentrated in
vacuo to afford the analytically pure 1-(p-toluenesulfonyloxy)-1,2-
benziodoxol-3(1H)-one in 93% yield. Spectral data of 1-(p-toluene-
sulfonyloxy)-1,2-benziodoxol-3(1H)-one 8: 1H NMR (DMSO):
d = 2.35 (s, 3H, ArCH3), 7.16 (d, 2H, J = 7.88 Hz, ArH), 7.66 (d,
2H, J = 8.08 Hz, ArH), 7.83 (t, J = 7.36 Hz, 1H, ArH), 7.98 (t,
J = 7.36 Hz, 1H, ArH), 8.15 (d, 1H, J = 7.48 Hz, ArH), 8.31 (d, 1H,
J = 7.88 Hz, ArH); 13C NMR (DMSO): d = 168.45, 146.58, 143.27,
138.9, 133.53, 132.85, 130.34, 130.10, 128.23, 125.53, 124.55, 20.91;
LCMS (M+1): m/z = 419.
12. (a) Kosser, G. F.; Wettach, R. H. J. Org. Chem. 1976, 41, 3609; (b)
Kosser, G. F.; Wettach, R. H. J. Org. Chem. 1976, 42, 176; (c) Kosser,
G. F.; Wettach, R. H. J.; Smith, C. S. J. Org. Chem. 1980, 45, 1542;
(d) Kosser, G. F.; Relenyi, A. G.; Kalos, A. N.; Rebrovic, L.;
Wettach, R. H. J. Org. Chem. 1982, 47, 2487; (e) Moriarty, R. M.;
Penmasta, R.; Awasthi, A. K.; Epa, W. R.; Prakash, I. J. Org. Chem.
1989, 54, 1101.
13. (a) Muraki, T.; Togo, H.; Yokoyama, M. J. Org. Chem. 1999, 64,
2883; (b) Muraki, T.; Togo, H.; Yokoyama, M. Synlett 1998, 286.
14. Experimental procedure for the a-tosyloxylation of ketones using 1-(p-
toluenesulfonyloxy)-1,2-benziodoxol-3(1H)-one: A mixture of appro-
priate ketone (1 mmol) and 1-(p-toluenesulfonyloxy)-1,2-benziodox-
ol-3(1H)-one 8 (1 mmol) was refluxed in CH3CN (10 mL) for the time
period shown in Table 1. After completion of reaction as ascertained
by TLC, the mixture was treated with aqueous sodium bicarbonate,
extracted with CH2Cl2, dried over anhydrous sodium sulfate,
concentrated under vacuum and subsequently chromatographed over
silica gel (230–400 mesh) using petroleum ether/ethyl acetate (4:1 v/v)
as eluent to afford the a-tosyloxylation product of the ketone.
Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.tetlet.
2008.03.119.
References and notes
1. (a) Wirth, T. Angew. Chem., Int. Ed. 2005, 44, 3656; (b) Moriarty, R.
M. J. Org. Chem. 2005, 70, 2893; (c) Stang, P. J. J. Org. Chem. 2003,
68, 2997; (d) Zhdankin, V. V.; Stang, P. Chem. Rev. 2002, 102, 2523;
(e) Moriarty, R. M.; Prakash, O. Org. React. 2002, 57, 327; (f)
Varvoglis, A. Hypervalent Iodine in Organic Synthesis; Academic
Press: London, 1997.
2. (a) Hartman, C.; Mayer, V. Chem. Ber. 1893, 26, 1727; (b) Katritzky,
A. R.; Savage, J. P.; Palenic, G. J.; Quian, K.; Zhang, Z.; Durst, H. D.
J. Chem. Soc., Perkin Trans. 1990, 2, 1657; (c) Dess, D. B.; Martin, J.
C. J. Am. Chem. Soc. 1991, 113, 7277; (d) Katritzky, A. R.; Savage, J.
P.; Gallos, J. K.; Durst, H. D. Org. Prep. Proced. Int. 1989, 21, 157;
(e) Frigerio, M.; Santagostino, M.; Sputore, S. J. Org. Chem. 1999,
64, 4537.
3. (a) Nicolaou, K. C.; Baran, P. S.; Zhong, Y.-L.; Barluenga, S.; Hunt,
K. W.; Kranich, R.; Vega, J. A. J. Am. Chem. Soc. 2002, 124, 2233;
(b) Nicolaou, K. C.; Montagnon, T.; Baran, P. S.; Zhong, Y.-L. J.
Am. Chem. Soc. 2002, 124, 2245; (c) Nicolaou, K. C.; Montagnon, T.;
Baran, P. S. Angew. Chem., Int. Ed. 2002, 41, 993; (d) Nicolaou, K.
C.; Gray, D. L. F.; Montagnon, T.; Harrison, S. T. Angew. Chem.,
Int. Ed. 2002, 41, 996; (e) Nicolaou, K. C.; Mathison, C. J. N.;
Montagnon, T. Angew. Chem., Int. Ed. 2003, 42, 4077.