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Iron-catalyzed unprecedented formation of benzo

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[d]imidazo[2,1-b]thiazoles under solvent-free

Cite this: RSC Adv., 2016, 6, 107225
conditions†
Sandip Gangadhar Balwe and Yeon Tae Jeong*
Received 29th September 2016
Accepted 4th November 2016
The unprecedented formation of benzo[d]imidazo[2,1-b]thiazole during iron-catalyzed coupling of 2-
aminobenzothiazole, aldehydes with nitroalkane in air has been observed. This unique transformation
DOI: 10.1039/c6ra24183b
possibly occurs through a sequential aza-Henry reaction and subsequent intramolecular cyclization,
www.rsc.org/advances followed by denitration. A variety of substituted benzo[d]imidazo[2,1-b]thiazole are obtained using this protocol.

Nowadays increasing number of applications of multicom-

1. Introduction ponent reactions (MCRs) are reported in medicinal chemistry,
In the family of heterocyclic compounds, sulfur and nitrogen- combinatorial chemistry, natural product synthesis, agro-
containing fused heterocycles are an important class of chemistry and polymer chemistry.9 Importantly, they are being
compounds in medicinal chemistry.1 Various biologically active tailored and ne tuned for synthesizing various heterocyclic
synthetic compounds have ve-membered sulfur and nitrogen- scaffolds that is particularly useful in the preparation of diverse
containing heterocyclic rings in their structures. Thus, fused chemical libraries of bioactive molecules.10 The importance of
heterocyclic derivatives with benzo[d]imidazo[2,1-b]thiazole moie- nitroalkanes in organic synthesis is mainly due to their easy
ties are remarkably valuable in modern drug discovery pro- conversion into the corresponding nitronate anions because of
grammes. Benzo[d]imidazo[2,1-b]thiazole is one of the most the high electron-withdrawing power of the nitro group that
important fused bicyclic sulfur and nitrogen-containing heterocy- provides an outstanding enhancement of the hydrogen acidity
cles and a chemical building block in synthetic organic chemistry at the a-position (pKa MeNO2 ¼ 10). The nitro-Mannich (or aza-
(Fig. 1). Structural scaffolds have been described as privileged Henry) reaction, involving nucleophilic addition of a nitronate
structures and in particular, reported to be associated with prom- species to an imines and related compounds is a powerful
ising biological activities such as antitumor agents,2 antimicrobial synthetic transformation that allows creation of a carbon–
agents,3 antibacterial agents,4 and antiallergic agents.5 Additionally carbon bond.11 Although various green solvents, such as ionic
these derivatives also have promised utilization for kinase inhibi- liquids and water, have been extensively studied, not using
tors6 and are active for PET imaging of Alzheimer's patients brains a solvent at all is denitely the best option, which makes the
as well as b-amyloid plaques.7 Therefore, high therapeutic prop- development of solvent-free reactions a high priority.12
erties of the benzo[d]imidazo[2,1-b]thiazole related drugs have As part of continuing research in our laboratory towards the
encouraged the organic chemists to synthesize a large number of development of a new reaction methodology, for the rst time
novel chemotherapeutic agents. But only a few methods have been herein, we disclosed a highly efficient, approach for the
developed so far for the synthesis of this scaffold.8 synthesis of functionalized benzo[d]imidazo[2,1-b]thiazole
Therefore, the availability of efficient and practical synthetic
routes to generate these heterocycles from basic and readily
available chemicals is in great demand. We envisaged that the
coupling between 2-aminobenzothiazole and aldehyde with
nitromethane would afford the benzo[d]imidazo[2,1-b]thiazole.
However, the unprecedented formation of benzo[d]imidazo[2,1-
b]thiazole was observed, possibly through the aza-Henry reac-
tion, cyclization and followed by denitration (Scheme 1).

Department of Image Science and Engineering, Pukyong National University, Busan

608-737, Republic of Korea. E-mail: ytjeong@pknu.ac.kr; Fax: +82-51-629-6408; Tel:
+82-51-629-6411
† Electronic supplementary information (ESI) available. See DOI: Fig. 1 Examples of biologically active benzo[d]imidazo[2,1-b]thiazole
10.1039/c6ra24183b derivatives.

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reaction was carried out in the presence of FeCl3 (10 mol%)

under aerobic conditions the unexpected formation of 2-
phenylbenzo[d]imidazo[2,1-b]thiazole was observed in 76%
yield within 6 h (Table 1, entry 2) and was conrmed by usual
spectroscopic techniques. Inspired by this result, we tested
various iron salts in salts like FeBr3, Fe(OAc)2, Fe(OTf)3, FeF3,
Scheme 1 Unprecedented formation of benzo[d]imidazo[2,1-b]thia- (Table 1, entries 3–6). The FeCl3 was found to be a more
zole (4). effective catalyst compared to other iron salts. Using copper
salt like Cu(OAc)2 under the identical conditions, failed to
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produce the product in any detectable amount (Table 1 entry

7). However, other common Lewis acids like AlCl3 and ZnCl2
were not effective for this reaction (Table 1, entries 8 and 9).
Next, we checked the effect of solvents; the yield was not
obviously increased in binary solvent systems such as nitro-
Scheme 2 Synthesis of benzo[d]imidazo[2,1-b]thiazole derivative methane with DMF, CH3CN, DMSO, and toluene, (Table 1,
catalyzed by FeCl3 under solvent-free condition. entries 10–14). To our delight, when the catalyst loading was
increased to 20 mol% of FeCl3 the signicant increment in
the yield (89%) was observed (Table 1 entry 15). Further
derivatives from 2-aminobenzothiazole, aldehydes, and nitro- increment in the catalyst loading was not found to be effec-
methane using a FeCl3 catalyst through a multicomponent tive (Table 1 entry 16). Similarly, increasing the temperature
cascade coupling (MCC) reaction under solvent free condition and time of the reaction did not showed improvement in the
with good to excellent yields (Scheme 2). yield (Table 1, entries 17 and 18). Unfortunately, when reac-
tion was carried out under optimized condition using nitro-
ethane, trace amount of product was formed (Table 1 entry
2. Results and discussion 19). Thus, optimal reaction conditions were obtained using
Initially, we examined the reaction of 2-aminobenzothiazole 2-aminobenzothiazole (1a, 1 mmol), benzaldehyde (2a,
(1a) and benzaldehyde (2a) in the absence of catalyst in 1.1 mmol) in presence of 20 mol% of FeCl3 in a nitro-
nitromethane (3a) at 80  C, but no desired compound was methane (3a, 3 ml) at 80  C (Table 1 entry 15) under aerobic
identied (Table 1, entry 1). Intriguingly, when the same condition.

Table 1 Optimization of the reaction conditions for 2-phenylbenzo[d]imidazo[2,1-b]thiazole (4a)a synthesis

Entry Catalyst (mol%) Solvent Temp ( C) Time (h) Yieldb (%)

1 — MeNO2 80 6 —
2 FeCl3 (10) MeNO2 80 6 76
3 FeBr3 (10) MeNO2 80 6 37
4 Fe(OAc)2 (10) MeNO2 80 6 Trace
5 Fe(OTf)3 (10) MeNO2 80 6 41
6 FeF3 (10) MeNO2 80 6 51
7 Cu(OAc)2 (10) MeNO2 80 6 —
8 AlCl3 (10) MeNO2 80 6 Trace
9 ZnCl2 (10) MeNO2 80 6 Trace
10 FeCl3 (10) MeNO2/DMF (1.5/1.5 ml) 80 8 67
11 FeCl3 (10) MeNO2/DMF 120 (1.5/1.5 ml) 8 70
12 FeCl3 (10) MeNO2/CH3CN (1.5/1.5 ml) 110 8 49
13 FeCl3 (10) MeNO2/DMSO (1.5/1.5 ml) 110 8 51
14 FeCl3 (10) MeNO2/Toluene (1.5/1.5 ml) 110 8 54
15 FeCl3 (20) MeNO2 80 6 89
16 FeCl3 (30) MeNO2 80 6 86
17 FeCl3 (20) MeNO2 80 12 87
18 FeCl3 (20) MeNO2 120 12 85
19 FeCl3 (20) EtNO2 80 8 Trace
a
Reaction conditions: 1.0 mmol of 1a, 1.1 mmol of 2a, FeCl3 (20 mol%), nitromethane (3a, 3 ml), 80 ( C), 6–8 h. b Isolated yield.

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Table 2 FeCl3 catalyzed one pot synthesis of benzo[d]imidazo[2,1-b]thiazole derivativesa

Entry R1 R Product Time (h) Yieldb (%) Mp ( C)

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1 C6H5 H 6 89 106–108

2 4-ClC6H4 H 6 91 160–162

3 4-BrC6H4 H 6 88 164–166

4 3-OMeC6H4 H 6 90 170–172

5 4-MeC6H4 H 6 94 147–149

6 C3H5 H 6 95 —

7 C4H7 H 6 93 —

8 C6H11 H 6 94 —

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Table 2 (Contd. )

Entry R1 R Product Time (h) Yieldb (%) Mp ( C)

9 2-C4H3S H 6 87 —
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10 C6H5 6-OCH3 6 93 —

11 4-ClC6H4 6-OCH3 6 88 158–160

12 4-BrC6H4 6-OCH3 6 92 161–163

13 3-OCH3C6H4 6-OCH3 6 90 —

14 4-CH3C6H4 6-OCH3 6 88 161–163

15 C4H7 6-OCH3 6 92 —

16 C6H11 6-OCH3 6 94 —

17 2-C4H3S 6-OCH3 6 88 —

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Table 2 (Contd. )

Entry R1 R Product Time (h) Yieldb (%) Mp ( C)

18 C6H5 6-CH3 6 90 158–160

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19 4-BrC6H4 6-CH3 6 89 178–180

20 3-OCH3C6H4 6-CH3 6 91 172–174

21 4-CH3C6H4 6-CH3 6 94 152–154

22 C3H5 6-CH3 6 94 —

23 C4H7 6-CH3 6 93 —

24 C6H11 6-CH3 6 90 —

25 2-C4H3S 6-CH3 6 88 —

26 3-OCH3C6H4 6-NO2 8 84 228–230

27 4-ClC6H4 6-F 8 89 162–164

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Table 2 (Contd. )

Entry R1 R Product Time (h) Yieldb (%) Mp ( C)

28 3-OCH3C6H4 6-F 8 86 168–170

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29 4-MeC6H4 4,6-F 8 90 216–218

30 3-MeC6H4 6-NO2 8 82 245–247

31 3-CF3C6H4 6-Me 8 89 —

a
Reaction of 2-aminobenzothiazole (1a, 1 mmol), aldehyde (2a, 1.1 mmol), nitromethane (3a, 3 ml), catalyzed by FeCl3 (20 mol%) under solvent-free
condition at 80  C. b Isolated yield.

With the optimized reaction conditions in hand, we explored the present protocol has general applicability, accommodating
the scope of this reaction (Table 2). a variety of substitution patterns.
Our attention was focused on the use of substituted alde- All the structure of synthesized compounds (4a-4ae) have
hydes and 2-aminobenzothiazole to prove the general applica- been ascertained on the basis of 1H NMR, 13C NMR and HRMS
bility of the reaction conditions (4a-4ae). Initially, the data.
substitution effect on the 2-aminobenzothiazole moiety was Some controlled experiments were carried out to understand
examined, various 2-aminobenzothiazoles having electron- the probable mechanistic path of this cyclization (Scheme 3).
donating and electron-withdrawing substituents like –Me, We synthesized the corresponding imine A by reacting with 2-
–OMe, –NO2, and halogens (–F), are tolerated well, and provided aminobenzothiazole (1a) and benzaldehyde (2a) in ethanol.
corresponding product in good to excellent yields under the When the imine A was subjected to the optimized reaction
optimized reaction condition. The chloro- and bromo- conditions, the corresponding 2-phenylbenzo[d]imidazo[2,1-b]
substituted benzaldehydes gave the corresponding products thiazole was obtained in quantitative yield (eqn (1)). Further-
in good yields respectively. Similarly, the aldehydes containing more, the imine A has been isolated from the reaction mixture
an electron donating –OMe group on the aromatic ring also by quenching the reaction aer 35 min. This suggests that the
showed good efficiency (4d, 4m, 4t, 4z, and 4ab). In addition, imine A is the key intermediate in this reaction. No signicant
heteroaryl aldehydes such as thiophene-2-carboxaldehyde could decrease in yield was observed when the reaction was carried
also participate in the multicomponent reaction to produce the out in the presence of a radical scavenger, TEMPO (1.5 equiv.)
desired products in good yields without affecting the heterocy- (eqn (2)) which favors the formation benzo[d]imidazo[2,1-b]
clic moieties (4i, 4q, 4y). However, aromatic aldehyde such as 3- thiazole through the non-radical mechanistic pathway.
hydroxybenzaldehyde and heteroaryl aldehydes pyrrole-2- From these controlled experiments the probable mechanism
carboxaldehyde and 2-pyridinecarboxaldehyde did not afford of the reaction is represented in Fig. 2.
the desired products. We were delighted to nd that the The rst step is the condensation between 2-amino-
aliphatic aldehydes such as cyclopropane-, cyclobutane- and benzothiazole and benzaldehyde imine A is formed. In the next
cyclohexanecarboxaldehyde also afforded the desired product step nucleophilic addition of nitromethane to the imine leads
with excellent yields (4f, 4g, 4h, 4o, 4p, 4v and 4w). Therefore, to the formation of intermediate B as aza-Henry product.

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open capillaries on an Electrothermal-9100 (Japan) instrument

and are uncorrected.

4.2 Synthesis of 2-phenylbenzo[d]imidazo[2,1-b]thiazole (4a)

A mixture of 2-aminobenzothiazole (1a, 1.0 mmol), and benz-
aldehyde (2a, 1.1 mmol), was dissolved in 3 ml of nitromethane
(3a) in a round-bottom ask, FeCl3 (10 mol%) was added, the
mixture was heated at 80  C until full consumption of 2-ami-
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Scheme 3 Controlled experiments. nobenzothiazole as monitored through TLC. Upon completion

(6–8 h) of the reaction, the mixture was ltered on Celite. The
ltrate was concentrated under reduced pressure to give the
crude material, which was puried by column chromatography
on silica gel (eluent:EtOAc/hexane) and afforded 2-phenylbenzo
[d]imidazo[2,1-b]thiazole (4a) in 89% yield. Compounds 4a-4ae
were also synthesized by adopting this procedure.

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