Letters in Organic Chemistry, 2012, 9, 155-159 155
1875-6255/12 $58.00+.00 © 2012 Bentham Science Publishers
Efficient Synthesis of 3-Aminoimidazo[1,2-a] Pyridines Using Silica-
Supported Perchloric Acid (HClO
4
-SiO
2
) as a Novel Heterogenous Catalyst
Azizollah Habibi*
,1
, Zahra Tarameshloo
1
, Shahnaz Rostamizadeh
2
and Ali M. Amani
2
1
Faculty of Chemistry, Tarbiat Moallem University, No. 43, Mofateh Avenue, Tehran, Iran
2
Department of Chemistry, Faculty of Sciences, K.N. Toosi University of Technology, Tehran, Iran
Received September 09, 2011: Revised January 16, 2012: Accepted January 17, 2012
Abstract: One pot three-component reaction of 2-amino pyridines, aldehydes and isocyanides in the presence of silica-
supported perchloric acid (HClO
4
-SiO
2
), produces 3-aminoimidazo[1,2-a] pyridines in excellent yields. The reaction time
is short and work up of reaction is very easy. New compounds were identified by IR,
1
H NMR,
13
C NMR and Mass
spectrum.
Keywords: 3-Aminoimidazo[1,2-a] pyridine, isocyanide, multi-component reaction, silica-supported perchloric acid (HClO
4
-
SiO
2
).
INTRODUCTION
Heterocyclic compounds are particularly interested in all
branches of chemistry especially in medicinal chemistry.
These classes of compounds are widely distributed in nature
and are essential to life. Extensive researches have been done
to discover new heterocyclic compounds and develop novel
methods. The imidazo[1,2-a]annulanes bearing pyridine,
pyrazine and pyrimidine core constitute are an important
heterocycles which they show broadly biologically activities
such as anticytomegalo-zoster and antivaricella-zoster virus
[1], antifungal, antibacterial [2, 3], anti-inflammatory [4],
antiviral, antiulcer [5] and calcium channel blocker activities
[6]. Among new studies in 2007, Gudmundsson described
synthetic approach of novel imidazo[1,2-a] pyridines and
their anti-HSV activity [7, 8].
In recent years, considerable efforts have been devoted to
introduce new routes for the synthesis of imidazo[1,2-
a]pyridines and other analogs. An earlier method for the
synthesis of imidazo[1,2-a]pyridine is coupling of -
halocarbonyl compound with 2-amino pyridine. Although,
this reaction has been used for imidazo[1,2-a]annulated
pyrazines and pyrimidines, but has restricted for generation
of a diverse library of this heterocycles. Another one-pot
method is coupling of 2-amino annulated heterocycle,
sodium cyanide and formaldehyde which have limitation for
desired diversification in the molecules. These protocols
because of their restrictions could not be introduced as a
good general method.
RESULTS AND DISCUSSION
In recent years, significant isocyanide-based multi-
component reactions (ISMCRs) have been reported [9-11].
Multi-component reactions are important tools for the rapid
*Address correspondence to this author at the Faculty of Chemistry, Tarbiat
Moallem University, No. 43, Mofateh Avenue, Tehran, Iran; Tel/Fax: +98-
21-88848949; E-mail: habibi@tmu.ac.ir
and efficient synthesis of a wide variety of organic
molecules. In the usual organic chemistry, only a few MCRs
are known and each reaction produces compounds with
similar skeleton and only different substituent, whereas in
the chemistry of the isocyanides, a much greater variation of
MCRs is known and more different educts and products can
participate than the conventional reactions. Three-component
reaction of 2-amino pyridine, aldehyde and isocyanide was
performed in different situations and their results were
published in the literature. Some of these needs long time
[for instance, reaction in the presence of protic acid (AcOH,
HClO
4
)] [12] whereas reactions which were performed in the
presence of Lewis acid (Sc(OTf)
3
) [13] had complicated
work up procedure. Other synthetic routes for three
condensation reaction in the condition of solid acid
(montmorillonite clay K10 [14], (Sc (OTf)
3
) [13], solid
support {using isonitrile resin [3], resin bound aldehydes
[15] or immobilized acid [16]}; catalyst-free, in water [17];
synthesis in ionic liquid medium [18], application of
TMSCN as a non-classical isonitrile equivalent [19], were
recently reported. Table 1, shows differences in situation and
condition, time of reaction, simplicity of work up and finally
yields of reactions that recently reported. In spite of these
interesting and suitable methods [13-24], there is a need to
develop a facile route that can be easily used as a general and
efficient synthetic approach.
On the basis of information of Table 1, our procedure is a
fast, simple and has easily worked up procedure that we can
suggest as a general and efficient method for the synthesis of
imidazo[1,2-a]pyridines derivatives.
Here, we wish to report a three component condensation
of aldehyde 1, 2-aminopyridine 2 and isocyanide 3 in the
presence of silica-supported perchloric acid as catalyst
(Scheme 1).
This reaction was carried out at 70-90 ºC in a short time
and excellent yield (Table 2). New products (4d, 4f, 4g, 4h,
4i, 4j, 4l, 4n, 4o) were identified by IR,
1
H NMR,
13
C NMR
and Mass spectrum. The melting point and spectral data of