M-iodosylbenzoic acid as a convenient recyclable hypervalent iodine oxidant for the synthesis of α-iodo ketones by oxidative iodination of ketones

Article abstract of DOI:10.1055/s-0030-1258223

A convenient procedure for the preparation of -iodo ketones by oxidative iodination of ketones using iodine and m-iodosylbenzoic acid as a recyclable hypervalent iodine oxidant is reported. Various ketones and -dicarbonyl compounds can be iodinated by thi

Full text of DOI:10.1055/s-0030-1258223

PAPER
3681
m-Iodosylbenzoic Acid as a Convenient Recyclable Hypervalent Iodine Oxi-
dant for the Synthesis of a-Iodo Ketones by Oxidative Iodination of Ketones
m
-Iodosylbenzoic Acid
e
as
a
R
ecyc
h
lable
H
yper
m
valent Iodine Reage
a
nt n S. Yusubov,*a Rosa Y. Yusubova,a Tatyana V. Funk,a Ki-Whan Chi,b Andreas Kirschning,c
Viktor V. Zhdankin*d
a
The Siberian State Medical University and Tomsk Polytechnic University, 2 Moskovsky trakt, 634050 Tomsk, Russian Federation
E-mail: yusubov@mail.ru
University of Ulsan, 680-749 Ulsan, Republic of Korea
Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1b, 30167 Hannover, Germany
b
c
d
Department of Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA
Fax +1(218)7267394; E-mail: vzhdanki@d.umn.edu
Received 9 June 2010; revised 21 July 2010
present study, we wish to report the use of m-iodosylben-
Abstract: A convenient procedure for the preparation of a-iodo ke-
zoic acid as a convenient recyclable oxidant for the syn-
tones by oxidative iodination of ketones using iodine and m-iodo-
thesis of a-iodo ketones, which are important building
sylbenzoic acid as a recyclable hypervalent iodine oxidant is
reported. Various ketones and b-dicarbonyl compounds can be io-
blocks in organic synthesis.4 Previously reported methods
dinated by this reagent system under mild conditions affording the for the preparation of a-iodo ketones commonly employ
respective a-iodo-substituted carbonyl compounds in excellent
yields. The final products of iodination are conveniently separated
from byproducts by simple treatment with anionic exchange resin
oxidative iodination of carbonyl compounds using such
inconvenient and environmentally harmful reagents as se-
lenium dioxide,5a mercury(II) chloride,5b or cerium(IV)
ammonium nitrate.5c We have found that m-iodosylbenzo-
ic acid (1) (which actually has a polymeric structure)6 is
an excellent oxidizing reagent in the oxidative iodination
of ketones 3 whose reduced form, m-iodobenzoic acid (2),
can be removed at the end of the reaction by treatment
–
Amberlite IRA 900 HCO3 and are isolated with good purity after
evaporation of the solvent. The reduced form of the hypervalent io-
dine oxidant, m-iodobenzoic acid, can be recovered in 91–95%
yield from the Amberlite resin by treatment with aqueous hydro-
chloric acid followed by extraction with ethyl acetate.
Key words: halogenation, iodine, ketones, iodosylbenzene, m-io-
dosylbenzoic acid, hypervalent iodine
–
with anionic exchange resin Amberlite IRA 900 HCO3 5
producing pure a-iodo ketones 4 (Scheme 1).
AcOOH, AcOH
Hypervalent iodine reagents have emerged as the reagent
of choice for various synthetically useful oxidative trans-
formations.1 The most widely used reagents, (diacetoxy-
iodo)benzene, [hydroxy(tosyloxy)iodo]benzene, and
iodosylbenzene, are based on the oxidized form of iodo-
benzene, and the reactions of these reagents with organic
substrates lead to iodobenzene as the byproduct, which is
difficult to recover and reuse because of its high volatility
and solubility in organic solvents. Numerous research
groups have tried to improve iodobenzene-based hyperva-
lent iodine reagents by developing polymer-supported an-
alogues, such as, poly(diacetoxyiodo)styrene.2 Despite
the utility of polymer-supported reagents, they still have
several drawbacks. These reagents require multistep prep-
aration, they have lower reactivity compared to the corre-
sponding monomeric analogues, and, moreover, the
repeated use of these polymers leads to significant degra-
dation due to benzylic oxidation of the polystyrene chain.
HO2C
IO
HO2C
I
1
2
NMe3
HCO3
I2
HCl
O
O
5
R2
R2
R1
R1
NMe3
I
3
4
O2C
I
6
Scheme 1 Oxidative iodination of ketones using m-iodosylbenzoic
acid (1)
Recently, we have found that m-iodosylbenzoic acid3a,b
and its derivatives3c,d are efficient oxidizing reagents
whose reduced form, m-iodobenzoic acid, can be easily
recovered from the reaction mixture by treatment with an-
ionic exchange resin or by addition of NaHCO3.3 In the
The results for the iodination of various enolizable ke-
tones and b-dicarbonyl compounds are summarized in
Table 1. The iodination of ketones 3a–i (entries 1–9) was
performed by treatment with iodine and m-iodosylbenzoic
acid (1) in acetonitrile at 40–60 °C in the presence of cat-
alytic sulfuric acid. In the absence of strong acid this reac-
tion proceeds very slowly; the acid catalysis is essential
for activation of the polymeric reagent 1. The products of
iodination were separated from the acidic byproducts by
simple treatment with anionic exchange resin Amberlite
SYNTHESIS 2010, No. 21, pp 3681–3685
x
x.
x
x
.
2
0
1
0
Advanced online publication: 20.08.2010
DOI: 10.1055/s-0030-1258223; Art ID: M04210SS
© Georg Thieme Verlag Stuttgart · New York

3682
M. S. Yusubov et al.
PAPER
IRA 900 HCO3– 5 and isolated as NMR-pure compounds
after evaporation of the solvent. The iodination of aliphat-
ic ketones 3a and 3b afforded mixtures of mono- and di-
iodo ketones (entries 1 and 2), while cycloalkanones 3c,d
and alkylaryl ketones 3e–h selectively produced
monoiodo ketones in good yields (entries 3–8). Similar
selectivity has previously been reported for the oxidative
iodination of these ketones using other oxidants.7 The re-
action of 2-acetylthiophene (3i) under these conditions af-
forded exclusively the product of iodination in the
thiophene ring (entry 9), which is in agreement with liter-
ature data.8
Table 1 Oxidative Iodination of Ketones and b-Dicarbonyl Com-
pounds Using the Iodine/m-Iodosylbenzoic Acid Recyclable Reagent
Systema
O
R2
O
R1
1, I2
R2
R1
I
3
4
Entry Ketone
Productsb
Time Yieldc
(h) (%)
O
O
O
I
I
+
The iodination of b-dicarbonyl compounds 3j–p with io-
dine and m-iodosylbenzoic acid (1) (Table 1, entries 10–
16) occurred under milder conditions, at room tempera-
ture and without acid catalyst. The NMR-pure products
4j–p were separated from the byproducts in almost quan-
titative yields by treatment with Amberlite IRA 900
1
3
3
79
82
I
1.2:1
4a
4a'
3a
I
I
I
–
HCO3 5 and identified by comparison of their physical
+
O
O
O
2
properties and 1H NMR spectral data with those reported
in the literature.7g,9 All reactions, with the exception of 1-
phenylbutane-1,3-dione (3o), were performed in acetoni-
trile. The reaction of diketone 3o in acetonitrile non-selec-
tively produced two regioisomers; however, changing the
solvent to less polar dichloromethane resulted in the clean
formation of a single product 4o in excellent yield (entry
15). Some of the iodides 4 have low thermal stability and
are light sensitive. Particularly unstable is ethyl 1-iodo-2-
oxocyclopentanecarboxylate (4n), which was previously
reported to decompose completely on silica gel during
column chromatography.9b Our simple and fast separation
procedure involving Amberlite resin allows column chro-
matography to be avoided and makes possible the isola-
tion of pure compound 4n, as well as other unstable
iodides.
10:1
4b
4b'
3b
O
O
I
3
2
8
62
74
4c
3c
O
O
4
I
3d
4d
O
O
5
7
4
79
70
Ph
Ph
I
3e
4e
The reduced form of the hypervalent iodine oxidant, m-io-
dobenzoic acid (2), can be easily recovered in 91–95%
yield from the Amberlite resin 6 by treatment with aque-
ous hydrochloric acid followed by extraction with ethyl
acetate.
O
O
Br
6
7
Br
I
3f
4f
O
O
I
In conclusion, we have developed a convenient procedure
for the preparation of a-iodo ketones by oxidative iodina-
tion of ketones using iodine and m-iodosylbenzoic acid as
a recyclable hypervalent iodine oxidant. Various ketones
and b-dicarbonyl compounds can be iodinated by this re-
agent system under mild conditions affording the corre-
sponding a-iodo-substituted carbonyl compounds in
excellent yields. The final products of iodination are con-
veniently separated from byproducts by simple treatment
3
6
92
93
3g
3h
4g
4h
O
O
8
9
I
I
–
with Amberlite resin IRA 900 HCO3 and are isolated
24 81d
S
with good purity after evaporation of the solvent. The re-
duced form of the hypervalent iodine oxidant, m-iodoben-
zoic acid, can be recovered from the Amberlite resin by
treatment with hydrochloric acid.
I
S
O
O
3i
3j
4i
O
O
O
O
10
1
86
I
4j
Synthesis 2010, No. 21, 3681–3685 © Thieme Stuttgart · New York

PAPER
m-Iodosylbenzoic Acid as a Recyclable Hypervalent Iodine Reagent
3683
Table 1 Oxidative Iodination of Ketones and b-Dicarbonyl Com-
pounds Using the Iodine/m-Iodosylbenzoic Acid Recyclable Reagent
Systema (continued)
mmol) were added with stirring. The mixture was stirred at 50 °C
for 6 h (TLC monitoring) and then the mixture was cooled to 0 °C
and CH2Cl2 (10 mL) was added. Amberlite IRA 900 HCO3– (5, 5.8
g) was added in small portions and the mixture was stirred for 10–
20 min at 0 °C in the dark (TLC monitoring for complete disappear-
ance of 2). The Amberlite polymer 6 (containing absorbed I2 and all
acidic byproducts and excessive reagents) was removed by filtra-
tion and the soln was concentrated under reduced pressure to afford
NMR-pure 4h (0.721 g, 93%). Additional recrystallization of the
crude product (hexane–EtOAc, 10:1) afforded analytically pure
product 4h (0.665 g, 86%); mp 68.5–69.5 °C (Lit.7a,b 68–70 °C).
O
R2
O
R1
1, I2
R2
R1
I
3
4
Entry Ketone
Productsb
Time Yieldc
(h) (%)
I
1H NMR (500 MHz, CDCl3): d = 3.49 (dd, J = 18.5, 2.5 Hz, 1 H),
3.89 (dd, J = 18.5, 7.5 Hz, 1 H), 4.96 (dd, J = 7.5, 2.5 Hz, 1 H), 7.43
(m, 2 H), 7.66 (td, J = 8.0, 1.5 Hz, 1 H), 7.86 (d, J = 8.0 Hz, 1 H).
13C NMR (125 MHz, CDCl3): d = 19.2 (CH2), 39.6 (CHI), 125.1,
126.5, 128.2, 132.9, 135.6, 151.2 (Carom), 201.5 (C=O).
11
1
3
1
94
91
66
O
O
O
O
3k
4k
I
Recovery of m-Iodobenzoic Acid (2): The Amberlite polymer 6 was
washed with 5% aq NaHSO3 (15 mL) and then H2O (15 mL) and
concd aq HCl (9 mL) were added and the resulting suspension was
stirred for 10 min. The precipitation of white crystals of m-iodoben-
zoic acid (2) was observed. Sat. aq NaCl (15 mL) was added and the
resulting mixture was extracted with EtOAc (2 × 30 mL). The ex-
tract was dried and evaporated to afford crystalline m-iodobenzoic
acid (2) (0.453 g, 91% recovery).
O
O
O
O
12
3l
4l
O
O
O
O
13
O
O
O
I
3m
Iodinated products 4a–h were prepared by a similar procedure and
identified by comparison of their 1H NMR spectra (see below) with
the literature data. The reaction times and yields of crude products
are shown in Table 1. In each reaction m-iodobenzoic acid (2) was
easily regenerated (recovery up to 95%) from IRA 900 by treatment
with aq HCl and reused without additional purification.
4m
O
O
O
O
I
14
0.5 86
0.5 95e
0.5 97
O
3n
4n
O
O
O
O
O
3-Iodooctan-2-one (4a) and 1,3-Diiodooctan-2-one (4a¢)
Ratio 4a/4a¢ = 1.2:1; oil.
15
Ph
Ph
I
3o
3-Iodooctan-2-one (4a)
4o
1H NMR (300 MHz, CDCl3): d = 0.90 (t, J = 7.5 Hz, 3 H, CH3),
1.29–1.41 (m, 6 H, 3 CH2), 1.90–1.98 (m, 2 H, CICH2), 2.40 (s, 3
H, CH3), 4.44 (t, J = 7.5 Hz, 1 H, CHI).7c
O
O
O
16
Ph
Ph
Ph
Ph
I
3p
1,3-Diiodooctan-2-one (4a¢)
4p
1H NMR (300 MHz, CDCl3): d = 0.88 (t, J = 7.5 Hz, 3 H, CH3),
1.29–1.41 (m, 6 H, CH2), 1.90–1.98 (m, 2 H, CICH2), 4.35 (s, 2 H,
ICH2), 4.94 (t, J = 7.5 Hz, 1 H, CHI).
a Reaction conditions for 3a–i: I2, reagent 1, 2 M H2SO4, MeCN, 40–
60 °C; for 3j–p: I2, reagent 1, MeCN, r.t.
b All products were identified using comparison of their physical
properties and 1H NMR spectral data with those reported in the liter-
ature.7–9,
4-Iodononan-5-one (4b) and 4,6-Diiodononan-5-one (4b¢)
Ratio 4b/4b¢ = 10:1; oil.
c All yields listed in the table are preparative yields of NMR-pure io-
dinated products.
4-Iodononan-5-one (4b)
d Selective formation of diiodide 4i was observed when excess of I2
and reagent 1 (2.5 equiv) were used.
1H NMR (200 MHz, CDCl3): d = 0.89–0.99 (m, 6 H, 2 CH3), 1.28–
1.66 (m, 4 H, 2 CH2), 1.85–2.02 (m, 2 H, CH2), 2.39 (m, 2 H,
CICH2), 2.58–2.84 (m, 2 H, CH2CO), 4.46 (t, J = 7.4 Hz, 1 H,
CHI).7d
e CH2Cl2 was used as solvent.
4,6-Diiodononan-5-one (4b¢)
All melting points were determined using a Boetius melting point
apparatus and are uncorrected. H NMR spectra were recorded on
1H NMR (200 MHz, CDCl3): d = 0.89–0.99 (m, 6 H, 2 CH3), 1.28–
1.66 (m, 4 H, 2 CH2), 2.39–2.85 (m, 4 H, 2 CICH2), 4.99 (t, J = 7.4
Hz, 2 H, 2 CHI).7e
1
Bruker AM NMR spectrometers (200, 300, and 400 MHz) or Vari-
an Inova instrument (500 MHz) using TMS as internal standard. All
commercial reagents were ACS reagent grade and used without fur-
ther purification. m-Iodosylbenzoic acid (1) was prepared according
to a previously reported procedure.3a
2-Iodocyclohexanone (4c)
Oil.
1H NMR (500 MHz, CDCl3): d = 1.58–1.77 (m, 2 H, CH2), 1.98–
2.17 (m, 4 H, 2 CH2), 2.35 (m, 2 H, CH2), 4.68 (m, 1 H, CHI).7f
2-Iodoindan-1-one (4h); Typical Procedure for Oxidative Iodi-
nation of Ketones 3a–i
Indan-1-one (3h, 0.396 g, 3.0 mmol) and MeCN (10 mL) were
placed in a light-protected flask and then 2 M H2SO4 (0.450 g), I2
(0.407 g, 1.6 mmol), and m-iodosylbenzoic acid (1, 0.53 g, 2.0
2-Iodocyclopentanone (4d)
Oil.
Synthesis 2010, No. 21, 3681–3685 © Thieme Stuttgart · New York

3684
M. S. Yusubov et al.
PAPER
1H NMR (200 MHz, CDCl3): d = 1.91–2.58 (m, 6 H, 3 CH2), 4.52
3-Iodopentane-2,4-dione (4j)
Keto and enol tautomers; oil.
(m, 1 H, CHI).7g,h
1H NMR (500 MHz, CDCl3): d = 2.23 (s, 3 H, CH3 enol form), 2.50
(s, 3 H, CH3 enol form), 2.82 (s, 3 H, CH3 keto form), 5.03 (s, 1 H,
CHI keto form).7f
2-Iodo-1-phenylethanone (4e)
Oil.
1H NMR (200 MHz, CDCl3): d = 4.36 (s, 2 H, CH2I), 7.54 (d,
J = 7.5 Hz, 2 H, Ph), 7.62 (m, 1 Harom), 8.00 (d, J = 7.5 Hz, 2
Harom).7f,g
4-Iodo-2,6-dimethylheptane-3,5-dione (4k)
Keto and enol tautomers; oil.
1H NMR (500 MHz, CDCl3): d = 1.15–1.20 (m, 6 H, CH3 keto
form), 1.38 (d, J = 2.4 Hz, CH3 enol form), 3.05–3.12 (m, 2 H, CH
keto form), 3.44–3.52 (m, CH enol form), 5.37 (s, 1 H, CHI keto
form).
1-(4-Bromophenyl)-2-iodoethanone (4f)
Oil.
1H NMR (500 MHz, CDCl3): d = 4.36 (s, 2 H, CH2I), 7.65 (d,
J = 7.4 Hz, 2 Harom), 8.10 (d, J = 7.4 Hz, 2 Harom).7i
2-Iodo-2-methylcyclohexane-1,3-dione (4l)
Light-sensitive unstable oil.
1H NMR (200 MHz, CDCl3): d = 1.76–1.87 (m, 1 H), 2.04 (s, 3 H,
CH3), 2.25–2.35 (m, 1 H), 2.47–2.54 (m, 2 H, CH2), 3.42–3.50 (m,
2 H).
2-Iodo-3,4-dihydronaphthalen-1(2H)-one (4g)
Mp 76–78 °C (Lit.7a 77–78 °C).
1
H NMR (500 MHz, CDCl3): d = 2.12–2.18 (m, 1 H), 2.27–2.31
(m, 1 H), 2.87 (td, J = 17.0, 3.8 Hz, 1 H), 3.15 (ddd, J = 17.0, 10.0,
4.5 Hz, 1 H), 5.03 (td, J = 3.8, 0.7 Hz, 1 H), 7.30 (m, 1 Harom), 7.37
(m, 1 Harom), 7.50 (td, J = 7.5, 1.3 Hz, 1 Harom), 8.10 (dd, J = 7.5, 1.3
Hz, 1 Harom).
Ethyl 2-Iodo-3-oxobutanoate (4m)
Keto and enol tautomers; oil.
1H NMR (500 MHz, CDCl3): d = 1.3 (t, J = 7.5 Hz, CH2CH3 keto
and enol forms), 2.53 (s, 3 H, CH3 keto form), 2.72 (s, CH3 enol
form), 4.26 (q, J = 7.5 Hz, 2 H, keto form CH2CH3), 4.39 (q, J = 7.5
Hz, CH2CH3 enol form), 5.00 (s, 1 H, CHI keto form).7g
1-(4,5-Diiodothiophen-2-yl)ethanone (4i)
Mp 123–124 °C (Lit.8 123–124 °C).
1H NMR (500 MHz, CDCl3): d = 2.50 (s, 3 H, CH3), 7.44 (s, 1 H,
thiophene).
Methyl 1-Iodo-2-oxocyclopentanecarboxylate (4n)
2-Iodo-1,3-diphenylpropane-1,3-dione (4p); Typical Procedure
for Oxidative Iodination of Diketones 3j–p
Light-sensitive unstable solid.9b
1H NMR (200 MHz, CDCl3): d = 2.06–2.61 (m, 6 H, 3 CH2), 3.82
(s, 3 H, CH3).
1,3-Diphenylpropane-1,3-dione (3p, 0.224 g, 1.0 mmol) and MeCN
(3 mL) were placed in a light-protected flask and then I2 (0.130 g,
0.51 mmol) and m-iodosylbenzoic acid (1, 0.145 g, 0.55 mmol)
were added with stirring at 5 °C. The mixture was stirred at r.t. for
30 min (TLC monitoring) and then the mixture was cooled to 0 °C
and CH2Cl2 (3 mL) was added. Amberlite IRA 900 HCO3– 5 (1.5 g)
was added in small portions and the mixture was stirred for 10 min
at 0 °C in the dark. After that 2 additional portions of Amberlite
(each 0.1 g) were added (TLC monitoring for complete disappear-
ance of m-iodobenzoic acid; attention: any excessive amount of
Amberlite IRA 900 HCO3– 5 binds with the enol form of the iodi-
nated diketone and thus leads to reduced yields). The Amberlite
polymer 6 (containing absorbed iodine and all acidic byproducts
and excessive reagent 1) was removed by filtration and the soln was
concentrated under reduced pressure to afford 4p (0.340 g, 97%) as
off-white crystals. Additional recrystallization of crude product
(hexane–CH2Cl2, 5:1, 10 mL) in a light-protected flask afforded an-
alytically pure 4p (0.322 g, 92%) as needles; mp 105–106 °C (Lit.9a
104–105 °C).
2-Iodo-1-phenylbutane-1,3-dione (4o)
Light-sensitive unstable solid.
1H NMR (200 MHz, CDCl3): d = 2.55 (s, 3 H, CH3), 5.95 (s, 1 H,
CHI), 7.50 (t, J = 7.5 Hz, 2 Harom), 7.62 (t, J = 7.5 Hz, 1 Harom), 7.96
(d, J = 7.5 Hz, 2 Harom).7g
Acknowledgment
V.V.Z. and M.S.Y are thankful to the Government of Russia for
support of their cooperative research program (FCP GK
02.740.11.5211; Zayavka 2010-1.5-000-010-044). V.V.Z. thanks
the National Science Foundation (research grant CHE-1009038) for
support of this research in the USA. K.W.C. and M.S.Y. are grateful
for the support of Brain Korea 21 program in Korea.
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Harom), 7.59 (m, 2 Harom), 7.98 (m, 4 Harom).
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washed with 5% aq NaHSO3 (5 mL) and then H2O (5 mL) and con-
cd aq HCl (3 mL) were added and the resulting suspension was
stirred for 10 min. The precipitation of white crystals of m-iodoben-
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resulting mixture was extracted with EtOAc (2 × 10 mL). The ex-
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acid (2) (0.130 g, 95% recovery).
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identified by comparison of their 1H NMR spectra (see below) with
the literature data. The reaction times and yields of crude products
are shown in Table 1. In each reaction m-iodobenzoic acid (2) was
easily regenerated (recovery up to 95%) from IRA 900 by treatment
with aq HCl and reused without additional purification.
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