Ceric ammonium nitrate as a convenient catalyst for protection of carbonyl compounds as 1,3-oxathianes

Article abstract of DOI:10.1081/SCC-120005996

A mild and efficient method for the protection of carbonyl compounds as 1,3-oxathianes has been established by the catalytic use of ceric ammonium nitrate at ambient temperature. While different types of aryl and alkyl ketones and aldehydes were protected

Full text of DOI:10.1081/SCC-120005996

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CERIC AMMONIUM NITRATE AS A CONVENIENT CATALYST
FOR PROTECTION OF CARBONYL COMPOUNDS AS 1,3-
OXATHIANES
a
b
Gourhari Maiti & Subhas Chandra Roy
a
Department of Chemistry , Jadavpur University , Jadavpur, Calcutta, 700032, India
b
Department of Organic Chemistry , Indian Association for the Cultivation of Science ,
Jadavpur, Calcutta, 700032, India
Published online: 16 Aug 2006.
To cite this article: Gourhari Maiti & Subhas Chandra Roy (2002) CERIC AMMONIUM NITRATE AS A CONVENIENT CATALYST FOR
PROTECTION OF CARBONYL COMPOUNDS AS 1,3-OXATHIANES, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 32:15, 2269-2273, DOI: 10.1081/SCC-120005996
To link to this article: http://dx.doi.org/10.1081/SCC-120005996
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 15, pp. 2269–2273, 2002
CERIC AMMONIUM NITRATE AS A
CONVENIENT CATALYST FOR
PROTECTION OF CARBONYL
COMPOUNDS AS 1,3-OXATHIANES
1
2,
Gourhari Maiti and Subhas Chandra Roy *
1
Department of Chemistry, Jadavpur University,
Jadavpur, Calcutta - 700032, India
2
Department of Organic Chemistry, Indian Association
for the Cultivation of Science, Jadavpur,
Calcutta - 700032, India
ABSTRACT
A mild and efficient method for the protection of carbonyl
compounds as 1,3-oxathianes has been established by the cat-
alytic use of ceric ammonium nitrate at ambient temperature.
While different types of aryl and alkyl ketones and aldehydes
were protected smoothly, cyclic aryl ketones and diaryl
ketones remained unaffected under the reaction conditions.
Key Words: Ceric ammonium nitrate; Protection; Carbonyl
compounds; 1,3-Oxathianes
The great significance of selective introduction and removal of protect-
ing groups in organic synthesis is well established. The success of the
*
Corresponding author. Fax: 91-33-473-2805; E-mail: ocscr@mahendra.iacs.res.in
269
2
DOI: 10.1081/SCC-120005996
Copyright & 2002 by Marcel Dekker, Inc.
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2
270
MAITI AND ROY
Table 1. CAN-Catalysed Protection of Carbonyl Compounds
Carbonyl
Compounds
Yield
b
(%)
a
Entry
1
Products
81
2
3
84
75
4
5
89
85
6
82
7
8
81
87
9
90
1
0
85
(
continued )

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PROTECTION OF CARBONYL COMPOUNDS
2271
Table 1. Continued
Carbonyl
Compounds
Yield
b
(%)
a
Entry
Products
1
1
No reaction
–
–
1
2
No reaction
1
3
No reaction
–
a
b
All are isolated yields and are not optimised. All compounds were characterised by
1
IR and H NMR spectral data by comparing with authentic samples.
[2]
methodology largely depends on the stability of the protecting groups
towards different acidic and basic reagents and how easily they can be
[
1]
installed and removed. The protection of a carbonyl group into mono-
thioacetal is widely used in multistep organic synthesis due to its general
[
2]
stability under both acidic and basic conditions. Moreover, 1,3-oxathiane
is a versatile synthetic reagent for carbon–carbon bond formations to act
[
3]
as an acyl anion equivalent. In spite of the synthetic importance of mono-
thioacetals, only a very few methods for their preparation have been devel-
[
2,4,5]
oped.
But many of these methods suffer from limitations of using
stoichiometric reagents or harsh reaction conditions and sometimes cumber-
some extraction procedure. So a mild and simple method is still desirable.
In recent years, ceric ammonium nitrate (CAN) has largely been used
as an efficient catalyst for the protection of various functional groups which
includes our successful achievement towards CAN catalysed protection of
[6]
alcohols as THP-ethers. Now we report here a mild and efficient method
for 1,3-oxathioacetalisation of carbonyl compounds by using a catalytic
amount of ceric ammonium nitrate. Both reaction conditions and work-
up procedures are mild, simple and convenient. Thus, when various
aldehydes or ketones were treated with slight excess of 2-mercaptoethanol
in acetonitrile in the presence of a catalytic amount of ceric ammonium
nitrate at ambient temperature, the corresponding oxathioacetals
were yielded in excellent yields. The results are summarised in Table 1. In
general, the reactions were completed within 10 h. Among various solvents

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2
272
MAITI AND ROY
attempted acetonitrile was found to be the best one. Most of the aryl and
alkyl ketones and aldehydes underwent smooth conversion to monothio-
acetals, except the cyclic aryl ketones and diaryl ketones. Thus, indanone
(
Entry 11), 6-methoxy-a-tetralone (Entry 12) and benzophenone (Entry 13)
remained unaffected under the reaction conditions even after prolonged
30 h) stirring.
In conclusion, the mild reaction conditions and simple work-up
(
procedures make this methodology an ideal protocol for the protection of
various aldehydes and ketones as 1,3-oxathianes.
General Procedure: A mixture of carbonyl compound (3 mmol),
2-mercaptoethanol (3.9 mmol) and CAN (0.3 mmol) in anhydrous acetoni-
trile (10 mL) was stirred at ambient temperature (30 C) for 10 h under N
ꢀ
2
atmosphere. The reaction mixture was diluted with water (20 mL) and aceto-
nitrile was removed under reduced pressure. The aqueous layer was
extracted with ether (3 Â 30 mL). The organic layer was washed with 5%
aqueous NaOH (3 Â 10 mL), brine (3 Â 15 mL) and dried (Na SO ).
2
4
Volatiles were removed under reduced pressure and the yellowish-brown
residue was chromatographed over silica-gel (10% ethyl acetate in petro-
leum ether) to afford the 1,3-oxathiane.
ACKNOWLEDGMENT
S.C.R. thanks the Department of Science & Technology, New Delhi
for financial assistance.
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PROTECTION OF CARBONYL COMPOUNDS
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Received in the UK April 14, 2000

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