Regeneration of carbonyl compounds by oxidative cleavage of oximes with NBS in the presence of β-cyclodextrin in water

Article abstract of DOI:10.1081/SCC-200034766

The conversion of different oximes to the corresponding carbonyl compounds was carried out at room temperature in good to high yields with N-bromosuccinimide in water in the presence of β-cyclodextrin.

Full text of DOI:10.1081/SCC-200034766

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Regeneration of Carbonyl
Compounds by Oxidative
Cleavage of Oximes with
NBS in the Presence of
β‐Cyclodextrin in Water
M. Somi Reddy a , M. Narender a & K. Rama Rao a
a Organic Chemistry Division‐I , Indian Institute of
Chemical Technology , Hyderabad, 500 007, India
Published online: 12 Jan 2011.
To cite this article: M. Somi Reddy , M. Narender & K. Rama Rao (2004)
Regeneration of Carbonyl Compounds by Oxidative Cleavage of Oximes with
NBS in the Presence of β‐Cyclodextrin in Water, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry,
34:21, 3875-3881, DOI: 10.1081/SCC-200034766
To link to this article: http://dx.doi.org/10.1081/SCC-200034766
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 21, pp. 3875–3881, 2004
Regeneration of Carbonyl Compounds
by Oxidative Cleavage of Oximes
with NBS in the Presence of
b-Cyclodextrin in Water
*
M. Somi Reddy, M. Narender, and K. Rama Rao
Organic Chemistry Division-I, Indian Institute of Chemical Technology,
Hyderabad, India
ABSTRACT
The conversion of different oximes to the corresponding carbonyl com-
pounds was carried out at room temperature in good to high yields with
N-bromosuccinimide in water in the presence of b-cyclodextrin.
Key Words: Oximes; NBS; b-Cyclodextrin; Biomimetic; Oxidative
cleavage; Water.
*
Correspondence: K. Rama Rao, Organic Chemistry Division-I, Indian Institute
of Chemical Technology, Hyderabad 500 007, India; Fax: þ91-40-27160757;
E-mail: drkrrao@yahoo.com.
3875
DOI: 10.1081/SCC-200034766
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

3876
Reddy, Narender, and Rao
INTRODUCTION
Regeneration of carbonyl compounds from oximes is of great significance
in synthetic organic chemistry, since oximes can be prepared both from carbo-
nyl and noncarbonyl precursors.[1] They are utilized in the purification and
characterization of carbonyl compounds as well as in a variety of organic
reactions.[2] Therefore, regeneration of carbonyl compounds from stable
oximes under mild conditions is an important process. Various methods
reported to generate carbonyl compounds from oximes involve hydrolytic[3]
(acid-catalyzed), reductive,[4] oxidative,[5] clay supported ferric nitrite,[6]
microwave assisted,[7] N-halo amides,[8] manganese triacetate,[9] PCC,[10]
photochemical deprotection,[11] etc. However, only a few methods are avail-
able under mild conditions and hence, there is continued interest to explore
new methodologies, especially using water as a solvent. In our efforts to
develop biomimetic approaches through supramolecular catalysis with water
as a solvent involving cyclodextrins,[12] we have attempted the oxidative
cleavage of oximes with NBS in the presence of b-cyclodextrin (b-CD) in
water (Sch. 1).
RESULTS AND DISCUSSION
We report herein a new methodology for the deoximation of various
oximes (1) to carbonyl compounds (3) under supramolecular catalysis with
b-cyclodextrin using N-bromosuccinimide (2) in water. Cyclodextrins are
cyclic oligosaccharides, which exert microenvironmental effect. They cata-
lyze reactions by supramolecular catalysis through noncovalent bonding as
seen in enzymes. b-CD was used as a catalyst because it is easily accessible
and inexpensive among various cyclodextrins. N-bromosuccinimide has
Scheme 1.

Regeneration of Carbonyl Compounds by Oxidative Cleavage of Oximes 3877
been utilized as an effective deoximating agent under mild conditions to yield
carbonyl compounds in excellent yields.
These reactions were carried out by dissolving b-CD in water at room
temperature followed by the addition of oxime (1) and N-bromosuccinimide
(2). The yields of the products were impressive, ranging from 80% to 90%
(Table 1). It is also noteworthy that no over-oxidation to acids was observed.
It is also observed that the reaction times were extended in the absence of
b-CD. In a specific example, the reaction of 4-methyl benzaldoxime 4
(Table 1), which takes 20 min for completion in the presence of b-CD, was
extended up to 40 min in the absence of b-CD. b-Cyclodextrin was used
only in catalytic amount (0.1 mmol of CD per 1.0 mmol of the oxime).
Products were separated and purified by chromatographic techniques and
were also identified by IR, NMR, Mass spectroscopy, and by comparison
with the authentic samples.[13]
In conclusion, we have presented a simple methodology for the deprotec-
tion of a variety of oximes using NBS at room temperature with water as a
solvent under supramolecular catalysis.
EXPERIMENTAL SECTION
Materials
All reactions were carried out without any special precautions in an
atmosphere of air. Chemicals and solvents were purchased from Fluka
and S. D. Fine Chemicals and used as received. 1H NMR spectra were
obtained on a Gemini-200 or 300 MHz spectrometer. IR spectra were recorded
on a NICOLET FT-IR spectrometer. Mass spectra were observed on V. G.
Auto spectrometer. All oximes were prepared using standard synthetic
methods.[1]
General Procedure
To a solution of b-cyclodextrin (113.5 mg, 0.1 mmol) in distilled water
(15 mL) at room temperature was added the appropriate oxime (1.0 mmol) dis-
solved in acetone (2 mL), followed by the addition of N-Bromosuccinimide
(2.0 mmol). The reaction mixture was stirred at room temperature for
the specified time (Table 1). The product was extracted with ethyl acetate
(3 ꢀ 15 mL) and washed with brine solution. The combined organic phases

3878
Reddy, Narender, and Rao
Table 1. Oxidative cleavage of oximes with NBS in the presence of b-CD in water.
Entry
1
Substrate
Producta
Time (min)
25
% Yieldb
82
2
30
84
3
4
25
20
85
80
5
6
20
20
82
80
7
8
45
45
81
82
9
20
20
80
80
10
11
12
35
40
89
88
(continued)

Regeneration of Carbonyl Compounds by Oxidative Cleavage of Oximes 3879
Table 1. Continued.
Entry
13
Substrate
Producta
Time (min)
% Yieldb
45
87
14
50
87
15
16
25
25
90
90
17
25
87
18
19
20
25
84
90
aAll products were identified by IR, NMR, and mass spectroscopy.
bYields of products isolated after column chromatography.
were dried (Na2SO4) and concentrated under vacuum. The crude product thus
obtained was purified by column chromatography on silicagel (60–120 mesh)
using ethyl acetate: n-hexane (1 : 9).
ACKNOWLEDGMENT
We thank CSIR, New Delhi, India, for fellowships to MSR and MN.

3880
Reddy, Narender, and Rao
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Received in India June 21, 2004