A simple and efficient method for reductive acylation of azides using aluminium iodide and acetic anhydride

Article abstract of DOI:10.1081/SCC-120014976

A combination of aluminium iodide and acetic anhydride effectively converts a variety of azides to their corresponding acetamides in good to excellent yields without perturbing many active functionalities such as ether, ester, nitro etc.

Full text of DOI:10.1081/SCC-120014976

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A SIMPLE AND EFFICIENT METHOD FOR REDUCTIVE
ACYLATION OF AZIDES USING ALUMINIUM IODIDE AND
ACETIC ANHYDRIDE
Ghanashyam Bez a
a Department of Chemistry , Dibrugarh University , Dibrugarh, Assam, 786 004, India
Published online: 16 Aug 2006.
To cite this article: Ghanashyam Bez (2002) A SIMPLE AND EFFICIENT METHOD FOR REDUCTIVE ACYLATION OF AZIDES USING
ALUMINIUM IODIDE AND ACETIC ANHYDRIDE, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 32:23, 3625-3628, DOI: 10.1081/SCC-120014976
To link to this article: http://dx.doi.org/10.1081/SCC-120014976
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 23, pp. 3625–3628, 2002
A SIMPLE AND EFFICIENT METHOD FOR
REDUCTIVE ACYLATION OF AZIDES
USING ALUMINIUM IODIDE AND
ACETIC ANHYDRIDE
Ghanashyam Bez
Department of Chemistry, Dibrugarh University,
Dibrugarh-786 004, Assam, India
E-mail: ghanashyambez@yahoo.com
ABSTRACT
A combination of aluminium iodide and acetic anhydride
effectively converts a variety of azides to their corresponding
acetamides in good to excellent yields without perturbing
many active functionalities such as ether, ester, nitro etc.
Key Words: Reductive acylation; Azide; Acetamide; Alumi-
num iodide; Acetic anhydride
Introduction of an amino group into a carbon backbone, especially in
the field of the synthesis of natural products, is usually performed through
the substitution of azide anion for halogen like substitutents, followed
by reduction of azide functionality. Although numerous reports[1] on the
conversion of azides to amines are available in literature, an extensive
literature survey could provide only a few methods[2] for direct conversion
of azides to acylamines.
Keeping in view of developing a mild and chemoselective reagent
system, an attempt has been made to exploit the utility of relatively less
3625
DOI: 10.1081/SCC-120014976
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3626
BEZ
Table 1. Conversion of Azides to Acetamides
Reaction Time
(in min)
Entry
1
Substratea
Productb
% Yieldc
85
20
2
30
80
3
4
30
20
80
90
5
6
7
30
30
25
90
75
80
8
9
75
75
70
72
10
60
75
11
12
90
30
80
90
aAll azides were prepared by following standard literature procedures and charac-
terised by IR, MS and 1H NMR before performing the reactions; bAll products were
1
characterised by IR, MS and H NMR; Yields refer to pure isolated products.
c

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REDUCTIVE ACYLATION OF AZIDES
3627
explored and inexpensive reagent, AlI3 and acetic anhydride for direct
conversion of azides to acetamides. A number of observations (Entry
1–12 in Table 1) reveal that when an azide in acetonitrile is refluxed for
about half an hour with this reagent system, it undergoes excellent conver-
sion to acetamides. To the best of my knowledge, no such reagent system
has so far been reported for the reductive acylation of azide.
TYPICAL PROCEDURE
A freshly prepared solution of 1.3 g AlI3 (prepared by refluxing 1.2 g
aluminium foil and 17 g iodine in 40 mL dry acetonitrile till color of the
solution became pale yellow) in acetonitrile was added to a refluxing
solution of phenyl azide (1.3 g, 14.24 mmol) and acetic anhydride (2 mL)
in acetonitrile (2 mL) and allowed to reflux until completion while monitor-
ing the reaction by TLC. The temperature of the reaction mixture was
allowed to cool down to RT, and diluted with CHCl3 (10 mL), washed
successively with aqueous Na2S2O3 solution (20 mL) and brine. The organic
layer was separated, dried (over Na2SO4) and evaporated to get the crude
which was purified by column chromatography (EA/hexane ¼ 1.5).
Although AlI3 is an established ether cleaving agent,[3] the AlI3–acetic
anhydride combination is found to have little effect on ether (Entry 4) and
ester (Entry 2) functionalities under this reaction condition. Therefore this
method carries the preferences to the existing ones for being mild, selective
and cheap. This method provides a straightforward procedure for conver-
sion of azides to their corresponding acetamides in excellent yield avoiding
amino reduction and carboxylactivation usuayll required for two steps
conversion.
In conclusion, this reagent system describes one step conversion of
azides to acetamides using a easily made, cheap but excellent reagent system.
ACKNOWLEDGMENT
Author is grateful to Vice Chancellor, Dibrugarh University for
providing laboratory facilities for this work. Author is also grateful Dr.
N. C. Barua, Scientist, RRL, Jorhat, (India) for helpful discussion.

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3628
BEZ
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Received in the Netherlands November 22, 2001