Facile one-pot preparation of [hydroxy(sulfonyloxy)iodo]arenes from iodoarenes with MCPBA in the presence of sulfonic acids

Article abstract of DOI:10.1055/s-2005-872697

Various [hydroxy(sulfonyloxy)iodo]arenes were simply and efficiently obtained in high yields from the reaction of iodoarenes and MCPBA in the presence of sulfonic acids in a small amount of chloroform at room temperature, through a one-pot procedure. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-872697

2
486
LETTER
Facile One-Pot Preparation of [Hydroxy(sulfonyloxy)iodo]arenes from
Iodoarenes with MCPBA in the Presence of Sulfonic Acids
a
a,b
F
Y
acile One-Pot Pre
u
paration of
[
k
H
ydroxy(sul
i
fonylox
h
y)iodo]aren
a
e
s
ru Yamamoto, Hideo Togo*
a
Graduate School of Science and Technology, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
b
Department of Chemistry, Faculty of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
E-mail: togo@faculty.chiba-u.jp
Received 7 July 2005
iodo)phenyl]methane
from
1,3,5,7-tetrakis(4-
Abstract: Various [hydroxy(sulfonyloxy)iodo]arenes were simply
and efficiently obtained in high yields from the reaction of iodoare-
nes and MCPBA in the presence of sulfonic acids in a small amount
of chloroform at room temperature, through a one-pot procedure.
iodophenyl)adamantane and tetrakis(4-iodophenyl)meth-
ane, respectively, with MCPBA in a mixture of dichlo-
romethane and acetic acid under diluted conditions at
5
room temperature. However, oxidative conversion of
Key words: Koser’s reagent, [hydroxy(sulfonyloxy)iodo]arene,
MCPBA, sulfonic acid, iodoarene, one-pot preparation
these iodoarenes to the corresponding (diacetoxyiodo)are-
ne derivatives with peracetic acid and sodium perborate in
acetic acid, respectively, which are the most general syn-
6
thetic methods of (diacetoxyiodo)arenes, gave disap-
The use of hypervalent iodines for organic synthesis has
1
pointing results. Generally, room temperature conditions
are required for the formation of [hydroxy(sulfonyl-
oxy)iodo]arenes from the reaction of (diacetoxyiodo)are-
nes with p-toluenesulfonic acid monohydrate, due to the
high reactivity of [hydroxy(sulfonyloxy)iodo]arenes, and
the results indicate the formation of (diacyloxyiodo)are-
nes from iodoarenes with MCPBA may proceed at room
temperature. Thus, we postulated that one-pot oxidative
conversion of iodoarenes with MCPBA in a small amount
of chloroform in the presence of sulfonic acid monohy-
drate at room temperature should proceed.
been investigated widely; in particular, (diacetoxy-
iodo)benzene, iodosylbenzene, and [hydroxy(tosyl-
oxy)iodo]benzene (Koser’s reagent) are the most popular
and useful trivalent iodine reagents for organic synthesis.2
Among them, [hydroxy(tosyloxy)iodo]benzene is an
efficient sole reagent for the direct a-tosyloxylation of
3
ketones, and is a precursor for the formation of alkynyl
2
c,o
phenyl iodonium tosylates.
a-Tosyloxyketones are
very important strategic precursors for the construction of
various heteroaromatics such as thiazoles, selenazoles,
oxazoles, imidazoles, pyrazoles, benzofurans, and
3
lactones. We have also studied synthetic uses of Practically, when iodobenzene was treated with MCPBA
[
hydroxy(tosyloxy)iodo]arenes,
1-(arenesulfonyl- (1.1 equiv) in the presence of p-toluenesulfonic acid
oxy)benziodoxolones, and poly[4-hydroxy(tosyloxy)io- monohydrate (1.1 equiv) in a small amount of chloroform
do]styrene for the construction of thiazoles, imidazoles, at room temperature for two hours, the corresponding
4
imidazo[1.2-a]pyridines, and 2,1-benzothiazines. How- [hydroxy(tosyloxy)iodo]benzene was successfully ob-
ever, generally, those [hydroxy(tosyloxy)iodo]arenes are tained quickly in 95% yield (Table 1, entry 1). Other
prepared via two steps: the initial oxidation of iodoarenes sulfonic acids, instead of p-toluenesulfonic acid mono-
with peracetic acid or sodium perborate (Na BO ) in ace- hydrate, were also used to provide the corresponding
2
3
tic acid with warming to form (diacetoxyiodo)arenes, and [hydroxy(sulfonyloxy)iodo]benzenes under the same
subsequent treatment of (diacetoxyiodo)arenes with p-tol- conditions in good yields (Table 1, entries 3–9). Other
uenesulfonic acid monohydrate in acetonitrile at room iodoarenes in the presence of p-toluenesulfonic acid
temperature, to provide [hydroxy(tosyloxy)iodo]are- monohydrate were also converted to the corresponding
1
,3a
nes. Therefore, an efficient, direct, and simple method [hydroxy(tosyloxy)iodo]arenes smoothly in good yields
for the preparation of [hydroxy(tosyloxy)iodo]arenes under the same conditions (Table 1, entries 10–15). When
from iodoarenes has long been desired. To our knowl- the reaction was scaled up (10 mmol of iodobenzene
edge, a one-pot synthesis of [hydroxy(tosyloxy)iodo]are- instead of 1 mmol), [hydroxy(tosyloxy)iodo]benzene was
nes from iodoarenes has not been reported to date. Herein, obtained again in quite good yield (Table 1, entry 2).
we would like to report a direct, simple, one-pot prepara-
1
-(Arenesulfonyloxy)benziodoxolones could also be ob-
tion of [hydroxy(tosyloxy)iodo]arenes from iodoarenes.
tained from o-iodobenzoic acid in a one-pot procedure.
Very recently, Kita et al. reported the successful Thus the initial oxidation of o-iodobenzoic acid with
preparation of novel 1,3,5,7-tetrakis[4-(diacetoxy- MCPBA in a small amount of chloroform for one hour at
iodo)phenyl]adamantane and tetrakis[4-(diacetoxy- 40 °C, and then the addition of p-toluenesulfonic acid
monohydrate and acetic anhydride to the reaction mixture,
which was further stirred for one hour at room tempera-
ture, gave 1-(arenesulfonyloxy)benziodoxolones in good
yields (Equation 1).
SYNLETT 2005, No. 16, pp 2486–2488
Advanced online publication: 21.09.2005
DOI: 10.1055/s-2005-872697; Art ID: U21605ST
0
4
.1
0
.2
0
0
5
©
Georg Thieme Verlag Stuttgart · New York

LETTER
Facile One-Pot Preparation of [Hydroxy(sulfonyloxy)iodo]arenes
2487
Table 1 One-Pot Preparation of [Hydroxy(sulfonyloxy)iodo]arenes
from Iodoarenes with MCPBA in the Presence of Sulfonic Acids
O SR
1
) MCPBA, CHCl3, 40 °C
) RSO3H, Ac2O, r.t.
3
I
2
I
O
MCPBA, RSO3H·H2O
OH
I
CO2H
Ar
I
Ar
O
CHCl3, r.t.
3
R = 4-CH3C6H4
72% (4o)
72% (4p)
O3SR
3-O2NC6H4
1
2
Yield (%)a
Equation 1
Entry
Ar–
RSO H
3
1
2
SO H
95 (2a)
99
3
added to the reaction mixture, and the resulting mixture was filtered
b
and the solids were washed with Et O to provide [hydroxy(tosyl-
2
Me
oxy)iodo]benzene (2a) in 95% yield (0.37 g). When precipitation
3
4
2
O N
SO H
87 (2b)
87 (2c)
3
does not occur smoothly, it is better to remove CHCl before the
3
addition of Et O.
2
3
f
Mp 132–135 °C (Lit. 135–138 °C).
SO H
3
1
H NMR (400 MHz, CDCl , TMS, one drop of CF CO H): d = 2.42
3
3
2
O2N
Cl
NO2
(
s, 3 H), 7.29 (d, J = 8.0 Hz, 2 H), 7.78–7.55 (m, 5 H), 8.22 (d,
5
SO H
88 (2d)
J = 8.0 Hz, 2 H).
3
2b
Mp 143–145 °C.
6
7
SO H
76 (2e)
98 (2f)
97 (2g)
3
–
1
IR (KBr): 570, 640, 880, 1200, 1350, 1536, 3460 cm .
1
H NMR (400 MHz, DMSO): d = 7.58–7.75 (m, 4 H), 8.01 (d,
SO H
3
J = 7.8 Hz, 1 H), 8.16–8.24 (m, 3 H), 8.32 (s, 1 H), 9.76 (s, 1 H).
2
c
8
9
MeSO H
3
7
Mp 151–154 °C (Lit. 152–153 °C).
c
Me
Me
80 (2h)
SO3H
2d
O
3
f
Mp 114–117 °C (Lit. 118–120 °C).
1
1
0
1
93 (2i)
2
e
Mp 95 °C.
–
1
IR (KBr): 680, 740, 1040, 1120, 1200, 1440, 3460 cm .
SO H
3
100 (2j)
1
H NMR (400 MHz, DMSO): d = 7.49–7.54 (m, 2 H), 7.59 (t,
Me
Me
J = 7.6 Hz, 2 H), 7.66–7.73 (m, 2 H), 7.83–7.99 (m, 3 H), 8.14 (s, 1
H), 8.21 (dd, J = 8.2, 1.2, 2 H), 9.75 (s, 1 H).
1
1
1
2
3
4
95 (2k)
85 (2l)
Me
2
f
3
f
CF3
Mp 126–128 °C (Lit. 127–128 °C).
2
g
75 (2m)
8
Mp 120–122 °C (Lit. 120–122 °C).
CF3
2
h
15
96 (2n)
9
Mp 116–117 °C (Lit. 118–120 °C).
Cl
2
i
a
b
c
Isolated yield.
Iodobenzene (10 mmol, 2.04 g).
S)-(+)-Camphor-10-sulfonic acid monohydrate was used.
Mp 97–99 °C.
IR (KBr): 595, 1050, 1200, 1740, 2950, 3450 cm–1.
(
1
H NMR (400 MHz, DMSO): d = 0.69 (s, 3 H), 0.98 (s, 3 H), 1.25
q, J = 9.0 Hz, 2 H), 1.72–1.87 (m, 2 H), 1.90 (t, J = 4.5 Hz, 1 H),
(
2
.21 (dt, J = 7.5, 3.4 Hz, 1 H), 2.34 (d, J = 14.7 Hz, 1 H), 2.65 (t,
We believe the present method is very useful for the direct J = 9.0, 1 H), 2.84 (d, J = 14.7, 1 H), 7.64–7.77 (m, 2 H), 7.82 (t,
J = 8.3 Hz, 1 H), 8.07–8.20 (m, 2 H), 8.35 (d, J = 8.3 Hz, 1 H), 8.72
preparation of various types of [hydroxy(tosyloxy)io-
do]arenes from iodoarenes, due to the potent synthetic
utility of Koser’s reagent.
(
d, J = 7.2 Hz, 1 H).
2
j
1
0
Mp 108 °C (Lit. 115–118 °C).
[Hydroxy(tosyloxy)iodo]arenes; Typical Procedure
To a mixture of iodobenzene (0.20 g, 1 mmol) and p-TsOH·H O
2
2
k
(
0.20 g, 1.1 mmol) in CHCl (1 mL), was added MCPBA (0.21 g,
11
3
Mp 107 °C (Lit. 107–110 °C).
6
5%, 1.1 mmol). The mixture obtained was stirred for 2 h at r.t.
under an argon atmosphere. After the reaction, Et O (5 mL) was
2
Synlett 2005, No. 16, 2486–2488 © Thieme Stuttgart · New York

2
488
Y. Yamamoto, H. Togo
LETTER
2
l
(3) Reviews: (a) Moriarty, R. M.; Vaid, R. K.; Koser, G. F.
Synlett 1990, 365. (b) Koser, G. F. Aldrichimica 2001, 34,
9. (c) Prakash, O.; Saini, N.; Sharma, P. K. Heterocycles
4
b
Mp 156–157 °C (Lit. 158–162 °C).
8
2
m
1994, 38, 409. Papers: (d) Neilands, O.; Karele, B. J. Org.
Chem. USSR (Engl. Transl.) 1970, 6, 885. (e) Koser, G. F.;
Wettach, R. H.; Troup, J. M.; Bertram, A. F. J. Org. Chem.
Mp 157–159 °C.
–
1
IR (KBr): 700, 1043, 1200, 1310, 1640, 3560 cm .
1976, 41, 3609. (f) Koser, G. F.; Wettach, R. H. J. Org.
1
H NMR (400 MHz, DMSO): d = 2.25 (s, 3 H), 7.11 (d, J = 7.8 Hz,
Chem. 1977, 42, 1476. (g) Koser, G. F.; Wettach, R. H.;
Smith, C. S. J. Org. Chem. 1980, 45, 1543. (h)Koser, G. F.;
Relenyi, A. G.; Kalos, A. N.; Rebrovic, L.; Wettach, R. H. J.
Org. Chem. 1982, 47, 2487. (i) Moriarty, R. M.; Penmasta,
R.; Awasthi, A. K.; Epa, W. R.; Prakash, I. J. Org. Chem.
2
H), 7.46 (d, J = 7.7 Hz, 2 H), 7.89 (t, J = 7.8 Hz, 1 H), 7.98 (t,
J = 7.7 Hz, 1 H), 8.11 (d, J = 7.7 Hz, 1 H), 8.75 (d, J = 7.7 Hz, 1 H),
1
0.02 (s, 1 H).
2
n
1
989, 54, 1101. (j) Moriarty, R. M.; Vaid, R. K.; Hopkins, T.
E.; Vaid, B. K.; Prakash, O. Tetrahedron Lett. 1990, 31,
01. (k) Tuncay, A.; Dustman, J. A.; Fisher, G.; Tuncay, C.
3
f
Mp 158–160 °C (Lit. 159–161 °C).
2
4
o
I. Tetrahedron Lett. 1992, 33, 7647. (l) Moriarty, R. M.;
Vaid, B. K.; Duncan, M. P.; Levy, S. G.; Prakash, O.; Goyal,
S. Synthesis 1992, 845. (m) Prakash, O.; Goyal, S. Synthesis
1
2
Mp 174–176 °C (Lit. 178–180 °C).
4
p
1992, 629. (n) Prakash, O.; Rani, N.; Goyal, S. J. Chem.
Mp 176–178 °C.
Soc., Perkin Trans. 1 1992, 707. (o) Prakash, O.; Saini, N.;
Sharma, P. K. Synlett 1994, 221. (p) Vrama, R. S.; Kumar,
D.; Liesen, P. J. J. Chem. Soc., Perkin Trans. 1 1998, 4093.
–
1
IR (KBr): 880, 1195, 1350, 1530, 1605, 2900 cm .
1
H NMR (400 MHz, DMSO): d = 7.61–7.72 (m, 2 H), 7.83 (d,
(
q) Lee, J. C.; Choi, Ju.-H. Synlett 2001, 234.
J = 7.4 Hz, 2 H), 7.92–8.03 (m, 3 H), 8.18 (dd, J = 7.9, 1.4 Hz, 1 H),
(
4) Monomer reagents: (a) Muraki, T.; Togo, H.; Yokoyama,
M. J. Org. Chem. 1999, 64, 2883. (b) Nabana, T.; Togo, H.
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Tetrahedron 1989, 45, 3299.
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Org. Chem. 1990, 55, 315.
8
.33 (s, 1 H).
Acknowledgment
Financial support from a Grant-in-Aid for Scientific Research (No.
1
Culture of Japan is gratefully acknowledged.
6655012) from the Ministry of Education, Science, Sports and
(
(
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Synlett 2005, No. 16, 2486–2488 © Thieme Stuttgart · New York