Deoximation of oximes with 2-iodylbenzoic acid in water in the presence of β-cyclodextrin

Article abstract of DOI:10.1055/s-2003-41448

Oximes of various aldehydes and ketones can be converted to the corresponding carbonyl compounds at room temperature in impressive yields with 2-iodylbenzoic acid in water in the presence of β-cyclodextrin.

Full text of DOI:10.1055/s-2003-41448

1
968
SHORT PAPER
Deoximation of Oximes with 2-Iodylbenzoic Acid in Water in the Presence of
1
b-Cyclodextrin
D
N
eoximation of
O
x
.
ime
s
in the
S
P
resenc
e
of
b
-
r
Cyclode
i
xtrin lakshmi Krishnaveni, K. Surendra, Y. V. D. Nageswar, K. Rama Rao*
Organic Chemistry Division-I, Indian Institute of Chemical Technology, Hyderabad-500 007, India
E-mail: drkrrao@yahoo.com
Received 30 May 2003; revised 26 June 2003
O
OH
Abstract: Oximes of various aldehydes and ketones can be con-
verted to the corresponding carbonyl compounds at room tempera-
ture in impressive yields with 2-iodylbenzoic acid in water in the
presence of b-cyclodextrin.
N-OH
I
O
O
β-CD / H2O / rt
+
R1
R
R1
R
O
1
2
3
Key words: oximes, 2-iodylbenzoic acid, b-cyclodextrin, water
Scheme 1
The reactions were carried out by dissolving b-cyclodex-
trin in water followed by the addition of oxime 1 and 2-
iodylbenzoic acid (2) at room temperature. The deoxima-
tion yields obtained were impressive ranging up to 96%.
The yields from oximes with an aromatic moiety were
comparatively better than that from the saturated ones.
This methodology is also compatible with functionalities
such as halo, nitro, hydroxy, methoxy, methylenedioxy,
isopropoxy, and conjugated double bonds (Table 1). b-
Cyclodextrin was used as a catalyst since it is easily acces-
sible and inexpensive among various cyclodextrins. b-CD
was used only in catalytic amounts. These deoximation
reactions do not take place in the absence of b-cyclodex-
trin.
There is a growing interest for generating carbonyl com-
pounds from oximes since these can be prepared from
noncarbonyl precursors as well as used for the protection
and purification of carbonyl compounds. In view of the
importance of deoximation, several methods have been
developed for the cleavage of oximes, such as acid-cata-
2
3
4
5
lyzed hydrolysis, oxidative, reductive, clay-supported
6
7
ferric nitrite, trimethylsilyl chlorochromate, titanium sil-
icalite-1, zirconium sulfophenyl phosphonate, N-halo-
amides, manganese triacetate, microwave assisted,
pyridinium chlorochromate, pyridinium chlorochro-
mate/H O , 2-iodylbenzoic acid/DMSO–THF, trime-
thylammonium chlorochromate, chromium trioxide/
chlorotrimethylsilane,
8
9
1
0
11
12
1
3
5
c
14
2
2
1
5
1
6
17
photochemical deprotection,
The role of CD appears to be to activate not only the
oxime but may also be forming a CD·2 complex through
hydrogen bonding, which then oxidizes the oxime to the
corresponding carbonyl compound. In these reactions, re-
duced 2-iodylbenzoic acid, i.e. 2-iodosobenzoic acid has
been recycled by oxidation to 2-iodylbenzoic acid.21 The
b-cyclodextrin has also been recovered and reused.
etc. Though different approaches have been reported with
various limitations such as hazardous reagents and sol-
vents, higher temperatures, longer reaction times, lower
1
8
yields, etc. no attempt has yet been made to involve su-
pramolecular catalysis, with water as solvent, which
would be environmentally benign. In our efforts to devel-
op biomimetic approaches through supramolecular catal-
1
9
ysis involving cyclodextrins,
we explored the In conclusion, this methodology, involving b-cyclodex-
deoximation of oximes using a mild and environmentally trin in water with 2-iodylbenzoic acid as an oxidizing
friendly oxidizing agent, catalyzed by cyclodextrins with agent, is the first of its kind to be developed for the deox-
water as solvent. Cyclodextrins are cyclic oligosaccha- imation of oximes and has several advantages over the ex-
rides, which exert a microenvironmental effect. They cat- isting methodologies.
alyze reactions by supramolecular catalysis through non-
covalent bonding as for example seen in enzymes.
Deoximation of Oximes; General Procedure
Amongst various oxidizing agents 2-iodylbenzoic acid
To a solution of b-cyclodextrin (113.5 mg, 0.1 mmol) in distilled
(
2), a hypervalent iodine reagent, attracted our attention
2
0
H O (15 mL) at r.t. was added the appropriate oxime (1 mmol) dis-
2
due to its low toxicity, and high selectivity. We report
herein the first examples of the deoximation of various
oximes 1 to carbonyl compounds 3 under supramolecular
solved in acetone (2 mL), followed by the addition of 2-iodylbenzo-
ic acid (280 mg, 1 mmol). The reaction mixture was stirred at r.t. for
1
2 h. The product was extracted with EtOAc (3 × 15 mL), the com-
catalysis with b-cyclodextrin (b-CD = cycloheptaamy- bined organic phases were dried (Na SO ) and concentrated under
2
4
lose) using 2-iodylbenzoic acid (2) in water (Scheme 1).
vacuum. The crude product thus obtained was purified by column
chromatography on silica gel (60–120 mesh) using EtOAc–hexane
(
9:1) and identified by IR spectra and by comparison with authentic
2
2
samples and known compounds.
SYNTHESIS 2003, No. 13, pp 1968–1970
1
8.
0
9
.
2
0
0
3
Advanced online publication: 10.09.2003
DOI: 10.1055/s-2003-41448; Art ID: Z07303SS.pdf
Georg Thieme Verlag Stuttgart · New York
©

SHORT PAPER
Deoximation of Oximes in the Presence of b-Cyclodextrin
1969
Table 1 Deoximation with 2-Iodylbenzoic Acid in Water in the
Presence of b-CD at Room Temperature
Table 1 Deoximation with 2-Iodylbenzoic Acid in Water in the
Presence of b-CD at Room Temperature (continued)
Producta
Yield (%)b
94
Entry Substrate
1
Producta
Yield (%)b
92
Entry Substrate
1
8
N-OH
O
N-OH
CHO
O
O
2
N-OH
CHO
CHO
96
94
96
89
Cl
Cl
19
20
N-OH
O
90
3
N-OH
Me
HO
HO
Me
4
N-OH
CHO
N-OH
O
94
84
MeO
O2N
MeO
5
N-OH
CHO
CHO
2
2
1
2
N-OH
O
O2N
6
N-OH
N-OH
90
91
90
82
HO
HO
7
8
MeO
CHO
OMe
MeO
N-OH
O
OMe
2
3
88
82
Me
Me
CHO
N-OH
O
N-OH
N-OH
N-OH
Me
O
Me
Me
O
Me
24
9
0
CHO
95
88
a
O
O
All Products were identified by IR, NMR, and mass spectroscopy.
Yields of products isolated after column chromatography.
b
1
1
CHO
Acknowledgment
1
85
N-OH
CHO
K S. thanks CSIR, New Delhi, India, for the award of a research fel-
lowship.
1
1
2
3
N-OH
CHO
85
95
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