β-cyclodextrin mediated synthesis of indole derivatives: reactions of isatins with 2-amino(or 2-thiole)anilines by supramolecular catalysis in water

Article abstract of DOI:10.1080/10610278.2018.1529315

An elegant, mild, and straightforward strategy for the synthesis of indole derivatives have been accomplished by the biomimetic catalysis for the first time in water under neutral conditions. This supramolecular catalyst oriented methodology provides a sustainable and green protocol for the synthesis of 6H-indolo[2,3-b]quinoxalines and 3H-spiro[benzo[d]thiazole-2,3’-indolin]-2’-one by the reaction of isatin derivatives with 1,2-difunctionalized benzene using β-cyclodextrin (β-CD) as a recoverable and reusable supramolecular catalyst.

Full text of DOI:10.1080/10610278.2018.1529315

Supramolecular Chemistry
ISSN: 1061-0278 (Print) 1029-0478 (Online) Journal homepage: http://www.tandfonline.com/loi/gsch20
β-cyclodextrin mediated synthesis of indole
derivatives: reactions of isatins with 2-amino(or
2-thiole)anilines by supramolecular catalysis in
water
Km Neha Shivhare & I. R. Siddiqui
To cite this article: Km Neha Shivhare & I. R. Siddiqui (2018): β-cyclodextrin mediated synthesis
of indole derivatives: reactions of isatins with 2-amino(or 2-thiole)anilines by supramolecular
catalysis in water, Supramolecular Chemistry, DOI: 10.1080/10610278.2018.1529315
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SUPRAMOLECULAR CHEMISTRY
https://doi.org/10.1080/10610278.2018.1529315
β-cyclodextrin mediated synthesis of indole derivatives: reactions of isatins with
2-amino(or 2-thiole)anilines by supramolecular catalysis in water
Km Neha Shivhare and I. R. Siddiqui
Laboratory of Green Synthesis, Department of Chemistry, University of Allahabad, Allahabad, India
ABSTRACT
ARTICLE HISTORY
Received 5 July 2018
Accepted 23 September 2018
An elegant, mild, and straightforward strategy for the synthesis of indole derivatives have been
accomplished by the biomimetic catalysis for the first time in water under neutral conditions. This
supramolecular catalyst oriented methodology provides a sustainable and green protocol for the
synthesis of 6H-indolo[2,3-b]quinoxalines and 3H-spiro[benzo[d]thiazole-2,3’-indolin]-2’-one by
the reaction of isatin derivatives with 1,2-difunctionalized benzene using β-cyclodextrin (β-CD)
as a recoverable and reusable supramolecular catalyst.
KEYWORDS
Supramolecular catalyst;
β-cyclodextrin;
chemoselectivity; indole
derivatives; heterocyclic
compounds
Introduction
Especially, much effort has been dedicated to catalytic
reactions utilizing supramolecular host systems (12).
Cyclodextrins and their derivatives assimilate guest mole-
cules of convenient size and shape into their sub-nanos-
caled cavities to form inclusion complexes in aqueous
media (13). Cyclodextrins obtained by enzymatic hydrolysis
of starch that comes from biomass (14). These are a family
of truncated-cone-like oligosaccharides of D-glucose units
linked in α (1-4) sequence and possessing hydrophobic-
hydrophilic cavities inside and outside respectively. These
cavities work as a host for the reactant molecules and act
like enzymes in their potential to bind starting materials (15,
16). Hence, By utilizing the substrate incorporation within
the cavities, cyclodextrins can catalyse a wide range of
chemical reactions as a supramolecular catalyst (12b,c, 17).
Cyclodextrins generally consist of 6, 7, or 8 D glucose
units referring to as α-, β-, and γ-CD respectively with
Organic synthesis aligned towards ‘Green Chemistry’
arouse developing interest in recent years resulting in
new environmentally benign strategies such as eco-
friendly solvent syntheses and reusable catalysts to save
resources and energy (1–3). Water, easily available, worth-
while and environmentally compatible green solvent is
considered as a probable substitution for the organic
solvents (4–10). In the continuation of our work towards
greener methodology for the synthesis of heterocyclic
compounds, we report the use of a biomimetic supramo-
lecular catalyst that is β-cyclodextrin (β-CD) for the C–N
and C-S bonds formation in aqueous reaction media.
During the past decades, a broad diversity of host-guest
and supramolecular systems have been tested to organic
synthesis, by virtue of their enormous potential for
adequately improving the reactivity and selectivity (11).
CONTACT I. R. Siddiqui
dr.irsiddiqui@gmail.com
Laboratory of Green Synthesis, Department of Chemistry, University of Allahabad, Allahabad, India
Supplemental data for this article can be accessed here.
© 2018 Informa UK Limited, trading as Taylor & Francis Group

2
K. N. SHIVHARE AND I. R. SIDDIQUI
some special merits such as readily accessibility, water
solubility, low toxicity and polyfunctionality (18). Among
them β-CD is the most commonly used due to its easiest
availability and low toxicity (Figure 1).
Result and discussion
We implemented the synthesis of indole derivatives using
(0.147g, 1 mmol) of isatin and (0.108g, 1 mmol) of o-phe-
nylenediamine using various reaction conditions. The
results were summarized in Table 1. The reaction tem-
perature was varied from room temperature to 60 °C and
80 °C. There was no product formation on varying the
reaction temperature until twelve hours (Table 1, entry
1–3) in the absence of the catalyst, this observation indi-
cated the significance of catalyst for the reaction to occur.
Because of being easily available and low toxic in nature,
β-cyclodextrin was tried first among α and γ-cyclodextrins.
Reaction temperature was optimized 60 °C in presence of
β-cyclodextrin having 15 mol% catalytic amount (Table 1,
entry 4–6). These entries explained that temperature has
more than one effect upon cyclodextrin inclusion com-
plexes. Heating can increase the solubility of inclusion
complex but also at the same time also destabilizes the
complex. Hence, these effects were balanced at 60 °C
temperature.
On further increase of the catalytic amount to
(20 mol%), there was no improvement in the yield
and also there was no drop on the reaction time
(Table 1, entry 7) whereas decrease in catalytic amount
to (10 mol%), reduce the yield of the product at this
temperature (Table 1, entry 8). Hence, it was concluded
that 60 °C was the suitable reaction temperature and
(15 mol%) was the ideal amount that we needed as a
catalyst for reaction condition.
The derivatives of indole exhibit both types of
activities pharmacologically as well as biologically
included anticonvulsant, anticancer, antiviral, and
antibacterial etc (19). Quinoxaline and indolo[2,3-b]
quinoxaline core moieties are credibly ubiquitous pri-
vileged heterocyclic scaffold to construct biologically
active compounds (20–22). In other applications, qui-
noxalines were used as semiconductors (23), dyes
(24), and as a desirable ligands in coordination chem-
istry (25). Biological activities of some indole deriva-
tives are shown in Figure 2 (26–30).
On the basis of common concept, synthesis of
indole derivatives involve the condensation reaction
of isatin derivatives with 1,2-difunctionalized benzene.
Figure 3 indicated that the reaction of isatin deriva-
tives with o-phenylenediamine had the possibilities to
form four kinds of product (3a, 3x, 3y and 3z) (31) but
chemoselectivity of reported greener protocol pro-
vided us only one desirable chemoselective product
(3a) with excellent yield (Figure 3).
Some procedures are reported in the literature for the
synthesis of 6H-indolo[2,3-b]quinoxalines (Figure 4) (32–
40). These reported methodologies produce good results
in many instances. However, some of the synthetic stra-
tegies suffer from metal catalyst, expensive reagents,
long reaction time, environmentally hazardous, harsh
reaction condition, tedious work-up procedure, unsatis-
factory yield and use of homogeneous catalyst, which
are difficult to separate from the reaction mixture and
reuse.
Finally when carried out β-cyclodextrin as catalyst in
various solvents such as methanol, ethanol, DCM, chloro-
form, acetonitrile and toluene (Table 1, entry 9–14).
However, β-cyclodextrin is insoluble in methanol ethanol
and other organic solvents so initially tried solvent, water
was concluded as best solvent for reaction condition.
Water has higher solubility of β-cyclodextrin at optimal
However, focusing on the concept of green metho-
dology, we are reporting a universal supramolecular
catalyst (β-CD) in reaction condition.
Figure 1. Chemical Structure of β-Cyclodextrin.

SUPRAMOLECULAR CHEMISTRY
3
Figure 2. Some important biologically active compounds having indole moieties.
temperature. Other cyclodextrins were also performed
like α- and γ-cyclodextrin (Table 1, entry 15–16) but
based on screening results in Table 1 β-cyclodextrin was
found ideal catalyst among others because we obtained
low conversions with either α- and γ-cyclodextrins. Hence,
It is transparent that cavity of α-cyclodextrin might be too
small to fit the reagents in cavities. In addition, the cavity
of γ-cyclodextrin was too big compare to α and β-cyclo-
dextrins. β-cyclodextrin has usually one order of degree,
higher affinity for the benzene derivatives as compared to
α- and γ-cyclodextrins.
6H-indolo[2,3-b]quinoxaline derivatives. Results of the
extended derivatives was shown in Table 2.
It was observed that the substitution pattern on isatin
played crucial role in governing the product yield. Isatin
with electron donating substituent decreases the product
yield whereas electron-withdrawing substituents increase
the product yield (Table 2, entry 10) due to electronic
factors associated with the functionality.
The plausible mechanism (41, 42) represents a typical
cascade of condensation followed by hydration and cycli-
zation in the cavity of β-cyclodextrin (Scheme 2). The supra-
molecular β-cyclodextrin have tendency to form inclusion
complex with isatin which is reported by Rama Rao (43) and
DFT study of o-phenylenediamine inclusion complex is
Under optimised condition (Scheme 1), the reaction
proceeds in the smooth way for various substituted
isatin derivatives with o-phenylenediamine to access

4
K. N. SHIVHARE AND I. R. SIDDIQUI
Figure 3. Chemoselective synthesis of indolo[2,3-b]quinoxaline derivatives.
Figure 4. Literature survey for synthesis of indoloquinoxaline derivatives.
reported by wang et.al (44). O-phenylenediamine spread
throughout into β-cyclodextrin from the upper edge with
an amino group and suspends into the cavity in parallel
with one of the amino groups. The amino group forms a
hydrogen bond with β-cyclodextrin, increasing the degree
of interaction. Therefore, β-cyclodextrin increases the
nucleophilicity of o-phenylenediamine and the electrophi-
licity of carbonyl carbon of isatin. Finally, the electron-rich

SUPRAMOLECULAR CHEMISTRY
5
Table 1. Optimatization of reaction condition for the synthesis of indolo[2,3-b]quinoxalinea.
Entry
Catalyst (mol%)
Solvent
Temperature (°C)
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
No Catalyst
No Catalyst
No Catalyst
Water
Water
Water
Water
Water
Water
Water
Water
Methanol
Ethanol
CH2Cl2
CHCl3
CH3CN
Toluene
Water
rt
12
12
12
6
4
4
4
6
4
5
8
8
8
8
4
4
NR
NR
NR
84
90
88
90
82
NR
60 °C
80 °C
40 °C
60 °C
80 °C
60 °C
60 °C
60 °C
70 °C
rt
50 °C
70 °C
70 °C
60 °C
60 °C
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (20 mol%)
β-CD (10 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
β-CD (15 mol%)
α-CD (15 mol%)
γ-CD (15 mol%)
9
10
11
12
13
14
15
16
38
Trace
Trace
22
Trace
40
Water
35
aReaction conditions: isatin (1 mmol) and o-phenylenediamine (1 mmol) with various rection conditions
bIsolated yield, rt = room temperature, NR = no reaction
Scheme 1. Synthesis of 6H-indolo[2,3-b]quinoxaline derivatives.
nitrogen atom attacks the carbon atom with positive
charges of the carbonyl group, completing nucleophilic
addition. The intermediate then generates Schiff’s base
through a dehydration reaction, resulting in 6H-indolo
[2,3-b]quinoxaline formation.
Obtained β-CD reused for further cycle. The catalytic
activity of the recycled catalyst was shown in Figure 5.
Conclusion
After completing of the reaction, mixture was cooled
to room temperature and mixture was extracted by
ethyl acetate (2 Â 30mL) and dried over anhydrous
sodium sulfate. Ethyl acetate removed in vacuum and
crude product obtained. The β-CD existing in aqueous
layer could be recycled easily by the mixing of acetone,
followed by the separation with centrifugation; how-
ever, the quantity of acetone added played a crucial
role for good recovery of β-CD. When the volume ratio
acetone: water reached to 2:1, 96% β-CD recovered.
In conclusion, a neutral aqueous phase facile and green
protocol for the synthesis of indolo derivatives has been
developed. In reported procedure, β-cyclodextrin is
used as biomimetic supramolecular catalyst with
green solvent water forming catalytic system. This is
an eco-friendly methodology with good green chemis-
try credentials, such as utilization of the minimum
amount of reusable, harmless supramolecular catalyst
and easy work-up procedure. These cyclodextrin-pro-
moted aqueous phase reactions as environmentally

6
K. N. SHIVHARE AND I. R. SIDDIQUI
Table 2. Substrate scope for formation of compound 3.
Isatin
Derivatives
1(a-k)
o-phenylene
diamine
(2)
Product
3(a-k)a
Time
(h)
Yield
(%)b
Entry
1
4
4
4
4
4
90
86
83
86
86
2
2
2
3
4
5
2
2
2
6
7
8
2
2
2
4
4
4
85
85
88
(Continued)

SUPRAMOLECULAR CHEMISTRY
7
Table 2. (Continued).
Isatin
Derivatives
1(a-k)
o-phenylene
diamine
(2)
Product
3(a-k)a
Time
(h)
Yield
(%)b
Entry
9
2
2
2
4
3
4
88
93
78
10
11
aAll products were characterized by IR,1H NMR, 13C NMR and mass spectroscopy,
bIsolatedyield of pure product.
Scheme 2. Plausible mechanism for the reaction.

8
K. N. SHIVHARE AND I. R. SIDDIQUI
Figure 5. Recyclability of the catalyst.
benign methodology may find worldwide application in
the field of organic and medicinal chemistry.
The resulting mixture was stirred and β-cyclodextrin
(15 mol%) was added to the solution. The reaction
progress was monitored using TLC by mixture of
Hexane – EtOAc (6/4). The completion of the reaction
as indicated by TLC in UV-chamber and vapour iodine
chamber. The reaction mixture was cooled to room
temperature and mixture was extracted by ethyl acet-
ate (2 Â 30mL) and dried over anhydrous sodium sul-
fate. Ethyl acetate removed in vacuum and crude
product obtained. To recycle β-cyclodextrin, acetone
was added in the aqueous media, β-cyclodextrin
recovered. Pure product (6H-Indolo[2,3-b]quinoxaline
3a) was obtained by silica gel column chromatography
(Hexane/EtOAc) = (7/3 – 6/4) as solid.
Experimental section
General information
Commercial reagents purchased from Aldrich and Alfa
1
Aesar and used without further purification. H and 13C
NMR spectra were recorded on a Bruker AVANCE 400
instrument using DMSO-d6 as solvent. Chemical shifts δ
are expressed in in parts per million (ppm) and internally
referenced to tetramethylsilane (TMS). Coupling constant, J
is reported in Hz. The following abbreviations were used:
s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.
Melting points were monitored by open glass capillary
method and were uncorrected. All the reaction procedures
were monitored by TLC using 40 pre-coated sheets of silica
gel G/UV-254 of 0.25mm thickness (Merck 60F254) and TLC
plates were visualized by exposure to ultraviolet light and/
or by exposure to iodine vapours and Product was obtained
by column chromatography performed on silica gel (60–
120 mesh). Infrared spectra were recorded on a perkin
Elmer FT-IR Spectrometer and reported in frequency of
absorption. Mass spectra were recorded on JEOL SX-102
(FAB) mass spectrometer at 70ev. Elemental analysis for C,
H, N were performed on Perkin Elmer model 2400 CHNS/O
analyzer at SAIF Chandigarh.
Preparation of 3H-spiro[benzo[d]thiazole-2,3’-
indolin]-2’-one (5)
To the solution of Isatin 1 (1 mmol) in water (20 ml) at room
temperature was added 2-aminobenzenethiol 4 (1 mmol)).
The resulting mixture was stirred and 15 mol% β-cyclodex-
trin catalyst was added in it. The reaction progress was
monitored using TLC by mixture of Hexane – EtOAc (7/3)
indicating the reaction was proceeding in well manner and
completed in 4 hours. After the reaction completion, pro-
duct was obtained via previous workup procedure and the
residue was subjected to silica gel column chromatography
to afford 3H-spiro[benzo[d]thiazole-2,3’-indolin]-2’-one 5 as
solid.
Methods of preparation
Preparation of 6H-indolo[2,3-b]quinoxaline
derivatives
Acknowledgments
Km Neha Shivhare gratefully thank to University Grant
Commission, New Delhi, India for the award of Junior
Research Fellowship and author is also thankful to SAIF,
To the solution of Isatin 1a (1 mmol) in water (20 ml)
at 60 °C was added o-phenylenediamine 2 (1 mmol).

SUPRAMOLECULAR CHEMISTRY
9
Punjab University Chandigarh for providing all the spectro-
scopic and analytical data.
M. J.; Ulmann, P. A.; Mirkin, C. A. Angew. Chem., Int.
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Disclosure statement
No potential conflict of interest was reported by the authors.
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