A One-Pot, Multicomponent Synthesis of 5′-Amino-2,2′-dioxospiro[indoline-3,3′-pyrrole]-4′-carbonitriles

Article abstract of DOI:10.1055/s-0035-1560963

A novel, one-pot, multicomponent synthesis of 5′-amino-2,2′-dioxospiro[indoline-3,3′-pyrrole]-4′-carbonitriles is described. The Knoevenagel condensation reaction between isatin derivatives and malononitrile gave the corresponding cyclic arylmethylidenema

Full text of DOI:10.1055/s-0035-1560963

SYNLETT
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©
Georg Thieme Verlag Stuttgart · New York
2016, 27, 383–386
383
letter
Synlett
M. Adib et al.
Letter
A One-Pot, Multicomponent Synthesis of 5′-Amino-2,2′-dioxo-
spiro[indoline-3,3′-pyrrole]-4′-carbonitriles
Mehdi Adib*a
Zahra Yasaeia
Peiman Mirzaeib
H N
2
R3
N
O
NC
R2
R2
CN
CN
pyridine
O
R3 NC
O
a
O +
+
School of Chemistry, College of Science, University of Tehran,
EtOH–H2O (1:1)
80 °C
P. O. Box 14155-6455 Tehran, Iran
madib@khayam.ut.ac.ir
Department of Chemistry, Shahid Beheshti University, Tehran,
N
N
R1
R1
2 examples
0–95% yields
b
1
7
Iran
Received: 17.08.2015
Accepted after revision: 20.10.2015
Published online: 11.12.2015
DOI: 10.1055/s-0035-1560963; Art ID: st-2015-d0643-l
N
O
H
O
N
N
OMe
Abstract A novel, one-pot, multicomponent synthesis of 5′-amino-
,2′-dioxospiro[indoline-3,3′-pyrrole]-4′-carbonitriles is described. The
Knoevenagel condensation reaction between isatin derivatives and
malononitrile gave the corresponding cyclic arylmethylidenemalononi-
triles that, on treatment with isocyanides, afforded 2,2′-dioxospiro-bis-
γ-lactams in good to excellent yields.
H
2
O
O
CO2Me
N
H
N
H
rhynchophylline
spirotryprostatin B
Key words isatins, isocyanides, spiro compounds, lactams, multicom-
ponent reactions
HO
O
Me
N
H
N
Cl
OH
F
MeO
Spiro[indoline-3,3′-pyrrole] motifs are found in many
natural products and biologically active synthetic com-
pounds. For example, indole alkaloids strychnofoline,
spirotryprostatin A, and spirotryprostatin B have been
shown to possess antimitotic properties, so are of interest
O
O
N
H
N
H
Cl
horsfiline
MI-219
1
Figure 1 Examples of natural products and synthetic molecules with a
spiro[indoline-3,3′-pyrrole] core structure
as anticancer drugs. Rhynchophylline is a noncompetitive
2
NMDA antagonist and calcium channel blocker, and hors-
3
filine presents analgesic effects. Synthetic compound
MI-219 is a potent, highly selective, and orally active inhib-
itor of the MDM2–p53 interaction, which has been studied
as a new agent for cancer treatment (Figure 1). A promi-
situ from Knovenagel condensation reaction of malononi-
trile and aromatic aldehydes were treated with quinoline
and cyclohexyl isocyanide under solvent-free conditions to
4
13
nent structural feature of all these natural and synthetic
products is the presence of a spiro[indoline-3,3′-pyrrole]
core. Thus, development of new approaches for the prepa-
ration of these spiro compounds have attracted a great deal
afford the corresponding pyrrolo[1,2-a]quinolines. We
were prompted to investigate whether isatin derivatives
could play the role of the carbonyl component in this multi-
component reaction, which would lead to a new skeleton.
Thus, a mixture of isatin 1a and malononitrile 2 were con-
densed at 100 °C under solvent-free conditions to give cy-
clic arylmethylidenemalononitrile 3 within 10 minutes.
Quinoline 4 and cyclohexyl isocynide 5a were then added
to the mixture, which was stirred at 100 °C for a further 24
hours. TLC monitoring of the reaction mixture indicated
formation of a new product (Table 1, entry 2), which was
purified. Identification of its structure by NMR spectrosco-
5–11
of attention.
In a continuation of our studies on the development of
efficient methods for the synthesis of biologically active
heterocyclic compounds from readily accessible precur-
12
sors, we have recently described a one-pot and four-com-
ponent synthesis of pyrrolo[1,2-a]quinoline-3-carboni-
triles. The 2-arylmethylidenemalononitriles generated in
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, 383–386

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M. Adib et al.
Letter
H2N
NC
NC
NC
CN
O
N
N
O
NC
4
CN
100 °C, 10 min
N
O
O
O
+
O
O
solvent-free
N
CN
N
N
N
NC 5a
H
H
H
H
1a
2
3
6a
7, not observed
solvent-free
00 °C, 24 h
1
Scheme 1 Condensation of isatin and malononitrile followed by treatment with quinoline and cyclohexyl isocynide
py revealed that it was 5′-amino-1′-cyclohexyl-2,2′-dioxo-
′,2′-dihydrospiro[indoline-3,3′-pyrrole]-4′-carbonitrile
6a), obtained in 20% yield and not the expected spiro[pyr-
of the reaction mixtures clearly indicated the formation of 6
in good to excellent yields.14 The results are summarized in
Table 2.
1
(
roloquinoline-2,3′-indoline] 7 (Scheme 1). However, further
investigations showed that the presence of quinoline in this
reaction was crucial; omission of the base led to a very low
yield of the product (entry 8). To improve the yield of 6a,
the effects of different bases, reaction temperatures, reac-
tion times and solvents were examined in this model reac-
tion, for which the reaction conditions would be optimized.
By varying the parameters, the highest yield was obtained
O
O
O
O
O
O
O
O
O
N
N
N
N
H
Me
Et
1
a
1b
NO2
1c
1d Bn
O
O
O
NC
NC
with one equivalent of pyridine as base, EtOH–H O (1:1) as
2
N
N
the reaction medium, at 80 °C after 20 hours; under these
conditions, 6a was obtained in 85% yield (entry 9).
H
1
e
1f
5a
5b
Figure 2 Starting materials for the multicomponent reaction
Table 1 Optimization of the Reaction Conditions for Synthesis of 6aa
Entry
Solvent
Base
quinoline
T (°C)
t (h)
Yield of 6a (%)b
The structures of the isolated products were deduced
1
13
on the basis of IR, H and C NMR spectroscopy, mass spec-
trometry, and elemental analysis. The IR spectrum of 6e
showed the stretching bands for N−H bonds at 3343, 3265,
and 3191, nitrile bond at 2187, and C=O bonds at 1739 and
1
2
3
4
5
6
7
8
9
CH
none
CH Cl
3
CN
reflux
100
reflux
60
24
24
24
24
24
6
trace
20
quinoline
quinoline
quinoline
quinoline
quinoline
quinoline
–
2
2
trace
trace
trace
70
–1
toluene
toluene
EtOH–H
EtOH–H
EtOH–H
EtOH–H
EtOH–H
EtOH–H
1667 cm . The mass spectrum of 6e displayed the molecu-
+
lar ion [M ] peak at m/z 364, which was consistent with the
reflux
60
1
:1:1 adduct of N-isopropylisatin (1e), malononitrile (2),
2
2
2
2
2
2
O
O
O
O
O
O
and cyclohexyl isocynide (5a). Fragment ions such as 321
80
20
20
20
20
20
82
+
+
+
+
[
(
M – C H ], 282 [M – C H ], 239 [M – (C H + C H ), M –
3
7
6
10
6
11
+
3
6
80
trace
85
+
C6H10 + C H ), or M – (NH C=NCy)], 212 [M – (NHC=NCy-
CO)], 197 [M – (CyN=C=O + C H ) or M – (Me CHN=C=O +
3
7
+
2
pyridine
DMAP
80
+
3
6
2
10
80
50
C H )] were consistent with the structure of 6e. The
6 12
1
H NMR spectrum of 6e exhibited characteristic multiplets
11
isoquinoline 80
83
at δ = 1.02–2.10 and 3.78–3.90 ppm for the cyclohexyl moi-
ety along with a doublet at δ = 1.39 ppm and a septet at δ =
a
Reaction conditions: isatin (1 mmol), malononitrile (1 mmol), cyclohexyl
isocynide (1.1 mmol), base (1 mmol).
b
Isolated yield.
4.49 ppm (J = 6.9 Hz) for the isopropyl group. Characteristic
signals were seen at δ = 7.02–7.35 ppm for the four protons
After optimization of the reaction conditions, to explore
the generality of the reaction, a series of 5′-amino-2,2′-di-
oxospiro[indoline-3,3′-pyrrole]-4′-carbonitriles 6 was pre-
pared from isatins 1a–f and isocynides 5a and 5b (Figure 2).
Thus, a mixture of isatin 1, malononitrile 2, isocynide 5,
of the phenylene moiety of the oxindole ring, as well as a
fairly sharp singlet at δ = 7.79 ppm for the NH group. The
2
1
13
H-decoupled C NMR spectrum of 6e showed characteris-
tic signals at δ = 19.4, 19.5, 25.0, 25.7, 29.0, 29.2, 44.6, and
53.0 ppm for the cyclohexyl and isopropyl substituents.
Distinguishing signals were observed at δ = 53.6 ppm for
the spiro-carbon atom, δ = 117.9 ppm for the nitrile group,
and δ = 171.9 and 172.1 ppm due to the two amide carbon-
and pyridine in EtOH–H O (1:1) was stirred at 80 °C for 20
2
or 24 h to afford the corresponding spiro[indoline-3,3′-pyr-
role] derivatives 6a–l. TLC and NMR spectroscopic analysis
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Table 2 Synthesis of 5′-Amino-2,2′-dioxo-1′,2′-dihydrospiro[indoline-3,3′-pyrrole]-4′-carbonitriles 6a–l
H2N
R3
NC
CN
N
O
NC
R2
R2
R2
CN
8
0 °C, 10 min
pyridine
O
O +
O
O
EtOH–H2O (1:1)
R3 NC
0 °C
5
N
R1
CN
N
N
R1
8
R1
1
2
3
6
Entry
R1
R2
R3
6
t (h)
Yield of 6 (%)a
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
Cy
6a
20
20
20
20
20
24
24
24
24
24
24
24
85
95
85
85
89
85
90
85
72
82
70
87
Me
Et
Cy
6b
6c
6d
6e
6f
Cy
Bn
i-Pr
H
Cy
Cy
NO
H
2
Cy
H
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
6g
6h
6i
Me
Et
H
H
10
Bn
i-Pr
H
H
6j
11
H
6k
6l
12
NO
2
a
Isolated yield.
yls of the two fused rings. Two other carbon atoms of the
pyrroline ring appeared as a shielded signal at δ = 61.6 ppm
and a deshielded signal at δ = 160.4 ppm (due to the C=CN2
carbon atoms, respectively), as well as six other distinct res-
onances (4 × CH and 2 × C) arising from the phenylene moi-
ety of the oxindole ring, in agreement with the proposed
ed system may undergo nucleophilic addition of the isocya-
nide 5 followed by protonation to form the positively
charged isonitrilium intermediate 8. The isonitrilium moi-
ety may undergo hydrolysis to produce amide intermediate
9. One of the nitrile groups of 9 can then undergo nucleop-
hilic addition of the adjacent amide functionality, which is
facilitated by the added base, to give the imino amide inter-
mediate 10. This imino amide can then tautomerize under
the reaction conditions to afford 5′-amino-2,2′-dioxo-
spiro[indoline-3,3′-pyrrole]-4′-carbonitriles 6.
14
structure.
A reasonable mechanistic rationalization for the forma-
tion of the spiro-bis-γ-lactams is provided in Scheme 2.
First, Knoevenagel reaction of isatin 1 and malononitrile 2
gives the condensation product 3. Next, the α,β-unsaturat-
In conclusion, we have developed a novel, one-pot and
multicomponent approach for the preparation of spiro[in-
doline-3,3′-pyrrole] derivatives. To our knowledge, this is
the first report of the synthesis of 2,2′-dioxospiro[indoline-
3,3′-pyrrole] derivatives with the two carbonyl functions
CN
_
H
NC
NC
CN
O
OH
5
_
C
+
+
N
R
N
R
1
+
2
O
15
located next to the spiro-carbon atom. The mild condi-
–
H2O
N
N
N
H
tions and good to excellent yields of the products are the
main advantages of this reaction. In view of the general bio-
logical activities of oxindoles and 2-pyrrolinones, combina-
tion of these structures in a single entity might lead to en-
hanced properties.
H
3
8
HN
H2N
R
R
NHR
N
NC
N
NC
NC
N
O
O
O
O
O
O
N
N
N
Acknowledgment
H
H
H
9
10
6
This research was supported by the Research Council of the Universi-
ty of Tehran.
Scheme 2 Proposed mechanism for the formation of 5′-amino-2,2′-
dioxospiro[indoline-3,3′-pyrrole]-4′-carbonitriles 6
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References and Notes
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(14) Preparation of Spiro[indoline-3,3′-pyrrole] Derivatives 6a–l;
Typical Procedure for 6a: A mixture of isatin (1 mmol) and
4
55, 27. (b) Kang, T. H.; Murakami, Y.; Takayama, H.; Kitajima,
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malononitrile (1 mmol) in H O–EtOH (1:1, 4 mL) was stirred at
2
80 °C for 10 min. Cyclohexyl isocyanide (1.1 mmol) and pyri-
3
dine (1 mmol) were added to the mixture, which was then
stirred at 80 °C for 20 h. Upon completion of the reaction, as
indicated by TLC, the mixture was cooled to room temperature,
brine (5 mL) was added, and the mixture was stirred for 5 min.
The product was extracted into EtOAc (3 × 5 mL), followed by
drying over Na SO . After filtration, the solvent was removed
(
3) (a) Jossang, A.; Jossang, P.; Hadi, H. A.; Sevenet, T.; Bodo, B.
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2
4
under the reduced pressure and the residue was crystallized
from EtOAc–n-hexane (1:1) to afford 6a as colorless crystals.
Compounds 6e and 6k were purified accordingly. Other
products were purified by column chromatography (EtOAc–
n-hexane, 1:4).
(5) (a) Lerchner, A.; Carreira, E. M. J. Am. Chem. Soc. 2002, 124,
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5′-Amino-1′-cyclohexyl-1-ethyl-2,2′-dioxo-1′,2′-dihydro-
8208.
spiro[indoline-3,3′-pyrrole]-4′-carbonitrile (6c): Yield: 0.298
g (85%); white crystals; mp 200–202 °C. IR (KBr): 3335, 3297
and 3185 (NH), 2191 (CN), 1735 and 1664 (C=O), 1600, 1453,
(6) Edmondson, S.; Danishefsky, S. J.; Sepp-Lorenzino, S.; Rosen, N.
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–1 1
1353, 1089, 999, 941, 832, 750, 680, 626 cm
. H NMR (300.1
MHz, DMSO-d ): δ = 1.05–2.10 [t, J = 7.1 Hz, 3 H, CH ; m, 10 H,
6
3
(c) Miyake, F. Y.; Yakushijin, K.; Horne, D. A. Angew. Chem. Int.
CH(CH ) ], 3.20–3.90 [q, J = 7.1 Hz, 2 H, CH ; m, 1 H, CH(CH ) ],
2
5
2
2 5
Ed. 2004, 43, 5357. (d) Meyers, C.; Carreira, E. M. Angew. Chem.
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7
7
.05–7.20 (m, 3 H, 3 × CH), 7.36 (t, J = 7.1 Hz, 1 H, CH), 7.80–
13
.89 (br. s, 2 H, NH2). C NMR (75.5 MHz, DMSO-d ): δ = 13.0
6
(CH ), 25.0 (CH ), 25.6 (2 × CH ), 28.9 and 29.1 (2 × CH ), 35.1
3
2
2
2
(CH ), 53.0 [CH(CH ) ], 53.3 (C−C=O), 61.6 (N C=C), 109.8 (CH),
2
2
5
2
1
1
17.9 (CN), 123.3 and 123.9 (2 × CH), 127.5 (C), 130.0 (CH),
(
8) Zhang, H.; Ma, X.; Kang, H.; Hong, L.; Wang, R. Chem. Asian J.
43.9 (C−N), 160.4 (N C=C), 171.8 and 172.0 (2 × C=O). MS: m/z
2
2013, 8, 542.
+
(
(
(
%) = 350 (42) [M ], 281 (48), 268 (100), 239 (42), 225 (34), 212
20), 198 (44), 183 (39), 160 (33), 128 (19), 97 (18), 83 (28), 69
34), 55 (80), 41 (80). Anal. Calcd for C20H22N O (350.41): C,
(
9) (a) Cravotto, G.; Giovenzana, G. B.; Pilati, T.; Sisti, M.; Palmisano,
G. J. Org. Chem. 2001, 66, 8447. (b) Murphy, J. A.; Tripoli, R.;
Khan, T. A.; Mali, U. W. Org. Lett. 2005, 7, 3287.
4
2
68.55; H, 6.33; N, 15.99. Found: C, 68.49; H, 6.37; N, 15.86.
(
10) (a) Zhang, B.; Feng, P.; Sun, L. H.; Cui, Y.; Ye, S.; Jiao, N. Chem.
Eur. J. 2012, 18, 9198. (b) Lv, H.; Tiwari, B.; Mo, J.; Xing, C.; Chi, Y.
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Zhu, G.; Wu, C.; Li, G.; Hong, L.; Wang, R. Angew. Chem. Int. Ed.
5
′-Amino-1′-cyclohexyl-1-isopropyl-2,2′-dioxo-1′,2′-dihy-
drospiro[indoline-3,3′-pyrrole]-4′-carbonitrile (6e): Yield:
.324 g (89%); white crystals; mp 196 °C. IR (KBr): 3343, 3265
and 3191 (NH), 2187 (CN), 1739 and 1667 (C=O), 1598, 1450,
0
–1
1
1306, 1230, 1171, 1092, 1001, 937, 808, 743, 677 cm . H NMR
(300.1 MHz, DMSO-d ): δ = 1.02–2.10 [d (1.39), J = 6.9 Hz, 6 H,
6
C(CH ) ; m, 10 H, CH(CH ) ], 3.78–3.90 [m, 1 H, CH(CH ) ], 4.49
3
2
2
5
2 5
2013, 52, 8633. (f) Tian, L.; Hu, X. Q.; Li, Y. H.; Xu, P. F. Chem.
(sept, J = 6.9 Hz, 1 H, CH), 7.02–7.13 (m, 2 H, 2 × CH), 7.25 (d, J =
Commun. 2013, 49, 7213. (g) Chen, X. H.; Wei, Q.; Luo, S. W.;
Xiao, H.; Gong, L. Z. J. Am. Chem. Soc. 2009, 131, 13819. (h) Shi,
F.; Tao, Z. L.; Luo, S. W.; Tu, S. J.; Gong, L. Z. Chem. Eur. J. 2012, 18,
6
.9 Hz, 1 H, CH), 7.35 (t, J = 6.9 Hz, 1 H, CH), 7.79 (s, 2 H, NH2).
13
C NMR (75.5 MHz, DMSO-d ): δ = 19.4 and 19.5 [C(CH ) ], 25.0
6
3 2
(CH ), 25.7 (2 × CH ), 29.0 and 29.2 (2 × CH ), 44.6 [C(CH ) ],
2 2 2 3 2
6
(
2
885. (i) Guo, C.; Song, J.; Gong, L. Z. Org. Lett. 2013, 15, 2676.
j) Liu, X. L.; Han, W. Y.; Zhang, X. M.; Yuan, W. C. Org. Lett.
013, 15, 1246.
53.0 [CH(CH ) ], 53.6 (C−C=O), 61.6 (N C=C), 110.9 (CH), 117.9
2
5
2
(CN), 123.0 and 124.1 (2 × CH), 127.8 (C), 129.9 (CH), 143.7
(C−N), 160.4 (N C=C), 171.9 and 172.1 (2 × C=O). MS: m/z (%) =
2
(
11) (a) Tan, B.; Zeng, X.; Leong, W. W. Y.; Shi, Z.; Barbas, C. F. III.;
Zhong, G. Chem. Eur. J. 2012, 18, 63. (b) Cao, Y.; Jiang, X.; Liu, L.;
Shen, F.; Zhang, F.; Wang, R. Angew. Chem. Int. Ed. 2011, 50,
+
364 (33) [M ], 321 (15), 282 (100), 239 (47), 212 (41), 197 (30),
170 (35), 143 (19), 128 (14), 116 (19), 105 (22), 81 (19), 67 (27),
55 (47), 41 (52). Anal. Calcd for C21H24N O (364.44): C, 69.21;
4
2
9
124.
12) (a) Adib, M.; Soheilizad, M.; Zhu, L. G.; Wu, J. Synlett 2015, 26,
77. (b) Adib, M.; Bayanati, M.; Soheilizad, M.; Janatian Ghaz-
vini, H.; Tajbakhsh, M.; Amanlou, M. Synlett 2014, 25, 2918.
H, 6.64; N, 15.37. Found: C, 69.18; H, 6.71; N, 15.30.
15) To our knowledge, there are two reports concerning the synthe-
sis of 2-oxo-2′-thioxospiro[indoline-3,3′-pyrrole] derivatives
with carbonyl and thiocarbonyl functions located next to the
spiro-carbon atom; see ref. 11.
(
(
1
(c) Mahernia, S.; Mahdavi, M.; Adib, M. Synlett 2014, 25, 1299.
(d) Adib, M.; Sheikhi, E.; Haghshenas, P.; Rajai-Daryasarei, S.;
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, 383–386