Facile synthesis of spiro[indane-2,1′-pyrrolo[2,1-a ]isoquinolines] via three-component reaction of isoquinolinium salts, indane-1,3-dione, and isatins

Article abstract of DOI:10.1055/s-0033-1340815

A series of novel 2′-aryl-2′-(2-oxo-1,2-dihydro-3H-indol-3- ylidene)-2′,3′-dihydro-10b′H-spiro[indene-2, 1′-pyrrolo[2,1-a]isoquinoline]-1,3-diones were efficiently synthesized by three-component reactions of in situ generated N-phenacylisoquinolinium bromides with indane-1,3-dione and isatins in ethanol with triethylamine as the base. A domino reaction mechanism for the formation of the spiro compounds was rationally proposed. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0033-1340815

PAPER
▌1059
paper
Facile Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines] via Three-
Component Reaction of Isoquinolinium Salts, Indane-1,3-dione, and Isatins
Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]
Xiao-Hua Wang, Chao-Guo Yan*
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, P. R. of China
Fax +86(514)87975244; E-mail: cgyan@yzu.edu.cn
Received: 24.12.2013; Accepted after revision: 22.01.2014
oxindole skeletons,12,13 which are the core structures of a
Abstract: A series of novel 2′-aryl-2′-(2-oxo-1,2-dihydro-3H-in-
large family of natural alkaloids and many pharmacologi-
dol-3-ylidene)-2′,3′-dihydro-10b′H-spiro[indene-2,1′-pyrrolo[2,1-
cal agents with important bioactivity and interesting struc-
a]isoquinoline]-1,3-diones were efficiently synthesized by three-
component reactions of in situ generated N-phenacylisoquinolinium
tural properties.14,15 In this practical field, we found that
bromides with indane-1,3-dione and isatins in ethanol with triethyl- the reactions of N-benzylbenzimidazolium salts, isatin,
amine as the base. A domino reaction mechanism for the formation
of the spiro compounds was rationally proposed.
and malononitrile gave a series of novel zwitterionic
salts.16 The 1,3-cycloaddition reactions of 3-phenacyli-
Key words: spiro compound, isoquinoline, isatin, indane-1,3-di-
one, nitrogen ylide, 1,3-cycloaddition
deneoxindoles with aza-aromatic N-ylides afforded a se-
ries of polycyclic spirooxindole systems.17 On the other
hand, similar cycloaddition reactions of pyridinium salts
and 4-(dimethylamino)pyridinium salts with 3-phenacyli-
Heteroaromatic N-ylides such as pyridinium, quinolini- deneoxindoles produced functionalized spiro[cyclopro-
um, and isoquinolinium methylides are readily available pane-1,3′-indolines], and 3-furan-3(2H)-ylideneindolin-
from the alkylations of aza-aromatic heterocycles and se- 2-ones depending upon the structures of the pyridinium
quential deprotonation reactions.1,2 The heteroaromatic salts and reaction conditions.18 Thus, the very interesting
N-ylides have been extensively used in cycloadditions for molecular diversity of the cycloaddition of heteroaromat-
the synthesis of various nitrogen-containing heterocy- ic N-ylides with isatin derivatives so far has prompted us
cles.3–9 In the past few years, we have successfully devel- to continue our investigation using the reactivity of other
oped several multicomponent reactions based on in situ substrates in these reactions. Here we wish to report the
formed reactive pyridinium salts and isoquinolinium salts unusual formation of novel 2′-isatylidenespiro[indane-
for the efficient synthesis of versatile heterocyclic com- 2,1′-pyrrolo[2,1-a]isoquinolines] [2′-aryl-2′-(2-oxo-1,2-
pounds.10,11 Recently, we envisioned that the 1,3-dipolar dihydro-3H-indol-3-ylidene)-2′,3′-dihydro-10b′H-spi-
cycloaddition reaction of heterocyclic N-ylides with isatin ro[indene-2,1′-pyrrolo[2,1-a]isoquinoline]-1,3-diones]
derivatives or 3-methyleneoxindoles would provide con- from the three-component reaction of isoquinolinium
venient methods for the construction of important spiro- salts, isatins, and indane-1,3-dione.
O
Ph
N
O
O
NH
O
Br
O
N
O
+
O
Et3N
2a
Ph
O
N
EtOH
H
N
O
NH
O
O
Br
O
N
OH
O
O
+
+
Ph
O
N
H
Ph
O
3a
Scheme 1 Synthesis of the spiro compound 3a via multicomponent reaction
SYNTHESIS 2014, 46, 1059–1066
Advanced online publication: 10.02.2014
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0033-1340815; Art ID: SS-2013-F0834-OP
© Georg Thieme Verlag Stuttgart · New York

1060
X.-H. Wang, C.-G. Yan
PAPER
We began our investigation by treating N-phenacyliso- dane-1,3-dione, and in situ generated N-phenacyliso-
quinolinium bromide (1a) with previously prepared 2-isa- quinolinium bromide (1a), from the reaction of
tylideneindane-1,3-dione19 in ethanol in the presence of isoquinoline and phenacyl bromide in the presence of tri-
triethylamine according to the previously established re- ethylamine, was heated at ca. 50 °C overnight. The func-
action conditions for the cycloaddition reactions used for tionalized
2′-isatylidenespiro[indane-2,1′-pyrrolo[2,1-
the efficient synthesis of functionalized spiro[indoline- a]isoquinoline] 3a was obtained in 85% yield (Table 1,
3,1′-pyrrolo[2,1-a]isoquinolines]17 (Scheme 1). After entry 1). Then under similar conditions, various isatins
workup, we were surprised to find that the expected 1,3- with 5-methyl, 5-fluoro, and 5-chloro groups and 1-ben-
dipolar cycloadduct 2a was not obtained. Instead, a new zyl and 1-butyl groups reacted smoothly with N-phen-
spiro compound 3a was prepared in moderate yield, in acylisoquinolinium
bromide
(1a)
and
N-(4-
which the moieties of isatin and indane-1,3-dione were chlorophenacyl)isoquinolinium bromide (1b) to afford a
not connected to each other. This result clearly indicated molecular library of spiro[indane-2,1′-pyrrolo[2,1-a]iso-
that a retro-aldol condensation of isatylideneindane-1,3- quinolines] 3b–q in satisfactory yields (entries 2–17, 72–
dione gave the starting substrates, indane-1,3-dione and 88%). These results clearly showed that the substituents in
isatin. Thus, the three-component reaction of N-phenacyl- isatins showed very little effect on the yields of products
isoquinolinium bromide (1a), isatin, and indane-1,3-dione and this new cycloaddition of isoquinolinium salts has a
was further investigated. An ethanol solution of isatin, in- wide substrate scope.
Table 1 Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]a
R1
O
O
O
R1
N
Et3N
Br
N
O
+
R2
N
+
EtOH, 50 °C
O
N
OH
O
R2
Ar
O
Ar
O
Entry
Product
Ar
R1
R2
Yield (%)
1
2
3a
3b
3c
3d
3e
3f
Ph
H
H
85
86
88
87
82
81
85
84
75
76
74
73
72
78
80
80
73
Ph
Me
F
H
3
Ph
H
4
Ph
Cl
H
H
5
4-ClC6H4
4-ClC6H4
4-ClC6H4
4-ClC6H4
Ph
H
6
Me
F
H
7
3g
3h
3i
H
8
Cl
H
H
9
Bn
Bn
Bn
Bn
Bn
Bu
Bu
Bu
Bu
10
11
12
13
14
15
16
17
3j
Ph
Me
Cl
F
3k
3l
Ph
Ph
3m
3n
3o
3p
3q
4-ClC6H4
Ph
F
F
Ph
Me
Cl
F
Ph
4-ClC6H4
a Reaction conditions: (a) 1. isoquinoline (1.2 mmol), phenacyl bromide (1.0 mmol), EtOH (10.0 mL), r.t., 1 h; 2. isatin (1.0 mmol), indane-
1,3-dione (1.0 mmol), Et3N (0.5 mmol), 50 °C, 12 h.
b Isolated yields.
Synthesis 2014, 46, 1059–1066
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]
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The structures of the spiro compounds 3a–q were charac-
1
terized by H and 13C NMR, HRMS, and IR spectra. A
typical structure, spiro compound 3e, was unambiguously
confirmed by single-crystal X-ray diffraction (Figure 1).
In the 1H NMR spectra of spiro compounds 3a–q, the CH
unit and the hydroxy group in the newly formed pyrrole
ring usually display two singlets at ca. δ = 5.70 and 8.70;
this indicates that only one stereoisomer predominately
exists in each sample of the spiro compounds 3a–q. In the
molecular structure of compound 3e, the newly formed
pyrrole ring assumes a slightly puckered envelope confor-
mation; the plane of the oxindole deviates from the pyr-
role ring. The phenyl group of the isatylidene moiety and
the isoquinoline ring are cis, that is the tetrasubstituted al-
kene is the E-isomer. It is clearly observed that the hydro-
gen atom and hydroxy group are trans. At present, we
tentatively propose that the prepared spiro compounds
3a–q exist in this configuration based on the 1H NMR data
and a single crystal structure.
Figure 1 Molecular structure of spiro compound 3e
To explain the formation of the spiro compounds, a reac-
tion mechanism for this domino three-component reaction
is proposed in Scheme 2. Firstly, N-phenacylisoquinolin-
ium bromide 1 is deprotonated by triethylamine to give a
isoquinolinium ylide A. Secondly, the condensation of
isoquinolinium ylide A with isatin gives isatylideneiso-
quinolinium salt B. Thirdly, the reaction of carbanion of
indane-1,3-dione with intermediate B affords adduct in-
termediate C, which in turn is deprotonated by triethyl-
amine to give another carbanion D. At last, the
intramolecular nucleophilic addition of carbanion to car-
bonyl group in the intermediate D and the protonation of
hydroxide ion results in the final spiro compound 3. Be-
cause there are no reactive carbonyl groups in the mole-
cules, similar reactions of N-(4-nitrobenzyl) or N-
[(ethoxycarbonyl)methyl]isoquinolinium bromides with
isatin and indane-1,3-dione only gave complex mixtures.
In order to explore the potential of this protocol for spiro-
heterocyclic synthesis, the three-component reaction of
isoquinolinium salts, acenaphthenequinone, and indane-
1,3-dione was also performed under similar reaction con-
ditions (Scheme 3). The corresponding 2′-acenaphthyli-
denespiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines] 4a,b
were obtained in 67% and 72% yields, respectively. This
result clearly indicated that this reaction has broad gener-
ality.
R1
O
R1
O
N
Br
R2
Et3N
N
N
N
R2
N
– HBr
– H2O
O
O
Ar
O
Ar
O
Ar
O
1
A
B
O
R1
R1
R1
N
N
N
Et3N
– H
N
R2
H
N
R2
N
R2
O
O
O
O
O
O
OH
O
O
Ar
O
Ar
Ar
O
O
3
D
C
Scheme 2 The proposed mechanism for the domino reaction
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 1059–1066

1062
X.-H. Wang, C.-G. Yan
PAPER
O
O
O
O
Br
N
N
O
Et3N
+
+
O
EtOH, 50 °C
O
OH
Ar
O
Ar
4a Ar = Ph, 67%
4b Ar = 4-ClC6H5, 72%
Scheme 3 Synthesis of 2′-acenaphthylidenespiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]
127.9, 126.4, 126.0, 125.2, 123.6, 122.9, 122.7, 122.0, 121.8, 120.8,
113.3, 109.6, 98.0, 88.5, 68.9, 63.3.
HRMS (ESI): m/z [M + Na]+ calcd for C34H22N2NaO4: 545.1472;
In summary, we have successfully found an unprecedent-
ed domino three-component reaction of isoquinolinium
salt, isatins and indane-1,3-dione. The reaction mecha-
nism involved the sequential condensation and cycloaddi-
tion reaction of an in situ generated isoquinolinium ylide.
This reaction provided a convenient procedure for the
synthesis of novel functionalized 2′-isatylidenespiro[in-
dane-2,1′-pyrrolo[2,1-a]isoquinolines] in good yields.
The short reaction time, readily variable substrates, and
easiness of handling render this domino reaction applica-
ble to the synthesis of structurally diverse heterocyclic
compounds.
found: 545.1471.
2′-(5-Methyl-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-phenyl-
Substituted 3b
Yellow solid; yield: 0.461 g (86%); mp 190–192 °C.
IR (KBr): 3136, 3027, 2965, 1745, 1710, 1650, 1620, 1593, 1556,
1487, 1459, 1426, 1326, 1273, 1235, 1216, 1188, 1149, 1064, 1000,
872, 816, 790, 750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.60 (s, 1 H, NH), 8.73 (s, 1
H, OH), 8.11–8.09 (m, 3 H, HAr), 7.99–7.98 (m, 1 H, HAr), 7.39–
7.35 (m, 4 H, HAr), 7.29 (s, 1 H, HAr), 7.25–7.22 (m, 3 H, HAr), 7.20
(d, J = 7.2 Hz, 1 H, HAr), 6.97–6.93 (m, 2 H, HAr), 6.78 (d, J = 7.8
Hz, 1 H, HAr), 6.58 (d, J = 7.8 Hz, 1 H, CH), 6.10 (d, J = 7.2 Hz, 1
H, CH), 5.63 (s, 1 H, CH), 2.33 (s, 3 H, CH3).
13C NMR (150 MHz, DMSO-d6): δ = 195.5, 195.0, 170.9, 159.1,
143.3, 141.9, 138.4, 138.3, 137.2, 136.6, 136.4, 131.2, 129.3, 129.1,
128.8, 128.7, 128.5, 128.4, 128.3, 127.8, 126.4, 126.0, 125.8, 123.6,
122.9, 122.8, 122.6, 122.0, 112.7, 109.3, 98.2, 88.4, 69.0, 63.2,
21.3.
All reactions were monitored by TLC. Melting points were taken on
a hot-plate microscope apparatus. IR spectra were obtained on a
Bruker Tensor 27 spectrophotometer (KBr disc). NMR spectra were
recorded with a Bruker AV-600 spectrometer with DMSO-d6 as sol-
vent and TMS as internal standard (600 and 150 MHz for 1H and 13
C
NMR spectra, respectively). HRMS (ESI) were obtained with a
Bruker MicroTOF spectrometer. X-ray data were collected on a
Bruker Smart APEX-2 CCD diffractometer. Single crystal data for
compounds 3e (CCDC 978440) have been deposited with the Cam-
bridge Crystallographic Data Centre.
HRMS (ESI): m/z [M + Na]+ calcd for C35H24N2NaO4: 559.1628;
found: 559.1624.
2′-(5-Fluoro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-phenyl-
Substituted 3c
2′-(2-Oxo-1,2-dihydro-3H-indol-3-ylidene)-2′,3′-dihydro-
10b′H-spiro[indene-2,1′-pyrrolo[2,1-a]isoquinoline]-1,3-diones
3a–q via Domino Three-Component Reaction; General Proce-
dure
A mixture of isoquinoline (1.2 mmol) and phenacyl bromide (1.0
mmol) in EtOH (10.0 mL) was stirred at r.t. for ~1 h. Then isatin
(1.0 mmol), indane-1,3-dione (1.0 mmol), and Et3N (0.5 mmol)
were added. The mixture was heated at 50 °C for overnight. After
cooling, the resulting precipitate was collected by filtration, and this
was recrystallized (EtOH–CHCl3) to give the pure product for anal-
ysis.
Yellow solid; yield: 0.476 g (88%); mp 206–208 °C.
IR (KBr): 3082, 2939, 2842, 1749, 1711, 1648, 1540, 1465, 1409,
1336, 1270, 1238, 1190, 1148, 1063, 1003, 960, 858, 819, 785 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.74 (s, 1 H, NH), 8.58 (s, 1
H, OH), 8.13–8.09 (m, 3 H, HAr), 7.99–7.93 (m, 1 H, HAr), 7.40–
7.36 (m, 4 H, HAr), 7.26–7.23 (m, 4 H, HAr), 7.19–7.17 (m, 1 H,
HAr), 6.99–6.93 (m, 2 H, HAr), 6.88–6.85 (m, 1 H, HAr), 6.67 (d,
J = 7.8 Hz, 1 H, CH), 6.11 (d, J = 7.8 Hz, 1 H, CH), 5.68 (s, 1 H,
CH).
2′-Phenyl-2′-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-Substitut-
ed 3a
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.9, 171.0, 160.4,
158.1, 156.5, 143.3, 142.0, 138.0, 137.2, 136.7, 134.9, 130.9, 129.3,
128.3, 128.1, 126.6, 126.0, 124.0, 123.6, 122.9, 122.1, 114.1, 111.3,
111.1, 110.1, 108.8, 108.6, 97.7, 88.5, 69.1, 63.4.
HRMS (ESI): m/z [M + Na]+ calcd for C34H21FN2NaO4: 563.1378;
found: 563.1379.
Yellow solid; yield: 0.443 g (85%); mp 202–204 °C.
IR (KBr): 3086, 3006, 2879, 2815, 1750, 1711, 1647, 1543, 1466,
1415, 1347, 1271, 1228, 1186, 1151, 1063, 1002, 974, 858, 785,
750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.71 (s, 1 H, NH), 8.63 (s, 1
H, OH), 8.13–8.09 (m, 3 H, HAr), 8.00–7.98 (m, 1 H, HAr), 7.46 (d,
J = 7.8Hz, 1 H, HAr), 7.39–7.36 (m, 4 H, HAr), 7.24 (q, J = 7.2Hz, 4
H, HAr), 7.13 (t, J = 7.8 Hz, 1 H, HAr), 7.03 (t, J = 7.8 Hz, 1 H, HAr),
6.96 (t, J = 7.8 Hz, 1 H, HAr), 6.89 (d, J = 7.8 Hz, 1 H, HAr), 6.60 (d,
J = 7.8 Hz, 1 H, CH), 6.10 (d, J = 7.2 Hz, 1 H, CH), 5.62 (s, 1 H,
CH).
2′-(5-Chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-phenyl-
Substituted 3d
Yellow solid; yield: 0.484 g (87%); mp 214–216 °C.
IR (KBr): 3130, 3062, 2836, 1746, 1710, 1649, 1548, 1461, 1334,
1303, 1272, 1228, 1186, 1147, 1062, 1001, 817, 792, 744 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.84 (s, 1 H, NH), 8.48 (s, 1
H, OH), 8.13–8.09 (m, 3 H, HAr), 8.00–7.98 (m, 1 H, HAr), 7.41–
7.37 (m, 5 H, HAr), 7.26–7.23 (m, 4 H, HAr), 7.16–7.14 (m, 1 H,
13C NMR (150 MHz, DMSO-d6): δ = 195.5, 195.0, 170.9, 159.3,
143.3, 141.9, 138.6, 138.1, 137.2, 136.6, 131.1, 129.2, 128.5, 128.3,
Synthesis 2014, 46, 1059–1066
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Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]
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HAr), 6.98 (t, J = 7.6 Hz, 1 H, HAr), 6.89 (d, J = 8.4 Hz, 1 H, HAr),
6.67 (d, J = 7.2 Hz, 1 H, CH), 6.12 (d, J = 7.8 Hz, 1 H, CH), 5.70 (s,
1 H, CH).
13C NMR (150 MHz, DMSO-d6): δ = 195.5, 194.8, 170.7, 160.4,
143.2, 142.0, 137.8, 137.3, 137.2, 136.7, 130.8, 129.2, 128.6, 128.4,
128.2, 128.1, 126.7, 125.9, 124.7, 124.5, 123.7, 122.9, 122.1, 121.2,
114.0, 110.7, 96.9, 88.5, 69.1, 63.4.
HRMS (ESI): m/z [M + Na]+ calcd for C34H20FClN2NaO4:
597.0988; found: 597.0982.
2′-(5-Chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-(4-chlo-
rophenyl)-Substituted 3h
Yellow solid; yield: 0.496 g (84%); mp 214–216 °C.
IR (KBr): 3126, 2995, 2837, 1743, 1708, 1654, 1554, 1464, 1433,
1401, 1333, 1303, 1271, 1229, 1187, 1149, 1093, 1001, 963, 872,
794, 751 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.88 (s, 1 H, NH), 8.57 (s, 1
H, OH), 8.14–8.10 (m, 3 H, HAr), 7.99–7.98 (m, 1 H, HAr), 7.45 (d,
J = 9.0 Hz, 2 H, HAr), 7.40 (d, J = 7.8 Hz, 2 H, HAr), 7.27–7.24 (m,
3 H, HAr), 7.21 (d, J = 7.2 Hz, 1 H, HAr), 7.16–7.15 (m, 1 H, HAr),
6.98 (t, J = 7.8 Hz, 1 H, HAr), 6.90 (d, J = 7.8 Hz, 1 H, HAr), 6.66 (d,
J = 7.8 Hz, 1 H, CH), 6.12 (d, J = 7.8 Hz, 1 H, CH), 5.73 (s, 1 H,
CH).
13C NMR (150 MHz, DMSO-d6): δ = 195.3, 194.9, 170.5, 159.7,
143.2, 141.8, 137.5, 137.0, 136.9, 136.8, 133.3, 130.7, 129.0, 128.7,
128.4, 128.2, 127.9, 127.8, 126.8, 124.8, 124.6, 124.3, 123.8, 123.0,
122.0, 121.2, 114.1, 110.8, 96.8, 87.8, 68.8, 63.4.
HRMS (ESI): m/z [M + Na]+ calcd for C34H21ClN2NaO4: 579.1082;
found: 579.1082.
2′-(4-Chlorophenyl)-2′-(2-oxo-1,2-dihydro-3H-indol-3-yli-
dene)-Substituted 3e
Yellow solid; yield: 0.456 g (82%); mp 191–192 °C.
IR (KBr): 3090, 2818, 1745, 1709, 1653, 1555, 1467, 1421, 1346,
1272, 1229, 1188, 1149, 1093, 999, 790, 750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.78 (s, 1 H, NH), 8.69 (s, 1
H, OH), 8.14–8.10 (m, 3 H, HAr), 8.00–7.99 (m, 1 H, HAr), 7.46–
7.44 (m, 3 H, HAr), 7.36 (d, J = 7.2 Hz, 1 H, HAr), 7.28–7.22 (m, 4
H, HAr), 7.12 (t, J = 7.8 Hz, 1 H, HAr), 7.03 (t, J = 7.8 Hz, 1 H, HAr),
6.97 (t, J = 7.8 Hz, 1 H, HAr), 6.90 (d, J = 7.8 Hz, 1 H, HAr), 6.60 (d,
J = 7.8 Hz, 1 H, CH), 6.10 (d, J = 7.8 Hz, 1 H, CH), 5.64 (s, 1 H,
CH).
HRMS (ESI): m/z [M + Na]+ calcd for C34H20Cl2N2NaO4: 613.0692;
found: 613.0681.
13C NMR (150 MHz, DMSO-d6): δ = 195.2, 195.1, 170.9, 158.7,
143.3, 141.9, 138.7, 127.4, 136.7, 133.2, 131.0, 129.1, 128.5, 128.3,
128.0, 127.9, 126.4, 125.3, 123.7, 122.9, 122.6, 122.1, 121.9, 113.3,
109.7, 98.0, 87.9, 68.8, 63.3.
HRMS (ESI): m/z [M + Na]+ calcd for C34H21ClN2NaO4: 579.1082;
found: 579.1081.
2′-(1-Benzyl-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-phenyl-
Substituted 3i
Yellow solid; yield: 0.459 g (75%); mp 212–214 °C.
IR (KBr): 3062, 2920, 1747, 1707, 1635, 1603, 1536, 1479, 1421,
1361, 1269, 1182, 1152, 1077, 1011, 976, 799 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.15–8.10 (m, 3 H, HAr), 8.00
(br s, 1 H, OH), 7.51 (d, J = 7.8 Hz, 1 H, HAr), 7.41–7.36 (m, 4 H,
HAr), 7.30–7.24 (m, 7 H, HAr), 7.21–7.17 (m, 3 H, HAr), 7.13 (t,
J = 7.2 Hz, 1 H, HAr), 7.07 (t, J = 7.2 Hz, 1 H, HAr), 7.03 (d, J = 7.2
Hz, 1 H, HAr), 6.97 (t, J = 7.2 Hz, 1 H, HAr), 6.62 (d, J = 7.8 Hz, 1
H, CH), 6.11 (d, J = 7.8 Hz, 1 H, CH), 5.68 (s, 1 H, CH), 4.86 (q,
J = 15.6 Hz, 2 H, CH2).
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.9, 168.8, 159.8,
143.2, 142.0, 138.8, 138.0, 136.7, 131.0, 129.2, 128.5, 128.4, 128.0,
126.5, 125.9, 125.0, 123.6, 123.0, 122.0, 121.9, 121.7, 121.5, 113.7,
109.1, 96.6, 88.6, 69.0, 63.3, 42.7.
2′-(4-Chlorophenyl)-2′-(5-methyl-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-Substituted 3f
Yellow solid; yield: 0.462 g (81%); mp 220–222 °C.
IR (KBr): 3134, 3025, 1742, 1708, 1684, 1652, 1556, 1488, 1460,
1428, 1338, 1272, 1235, 1217, 1186, 1148, 1092, 1001, 965, 872,
812, 789, 751 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.66 (s, 1 H, NH), 8.80 (s, 1
H, OH), 8.13–8.09 (m, 3 H, HAr), 7.99–7.98 (m, 1 H, HAr), 7.44 (d,
J = 8.4 Hz, 2 H, HAr), 7.37 (d, J = 7.8 Hz, 1 H, HAr), 7.29 (s, 1 H,
HAr), 7.26–7.23 (m, 3 H, HAr), 7.19 (d, J = 7.2 Hz, 1 H, HAr), 6.97–
6.93 (m, 2 H, HAr), 6.78 (d, J = 7.8 Hz, 1 H, HAr), 6.58 (d, J = 7.8
Hz, 1 H, CH), 6.10 (d, J = 7.2 Hz, 1 H, CH), 5.65 (s, 1 H, CH), 2.33
(s, 3 H, CH3).
13C NMR (150 MHz, DMSO-d6): δ = 195.2, 195.1, 170.9, 158.4,
143.3, 141.8, 137.5, 137.4, 136.4, 133.1, 131.1, 129.4, 128.9, 128.5,
128.3, 127.9, 126.5, 125.9, 123.7, 122.9, 122.7, 122.1, 112.7, 109.4,
98.2, 87.8, 68.8, 63.2, 21.3.
HRMS (ESI): m/z [M + H]+ calcd for C41H29N2O4: 613.2122; found:
613.2117.
2′-(1-Benzyl-5-methyl-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-
2′-phenyl-Substituted 3j
Yellow solid; yield: 0.476 g (76%); mp 218–220 °C.
IR (KBr): 3062, 2915, 1745, 1708, 1646, 1593, 1542, 1488, 1458,
1421, 1383, 1356, 1273, 1185, 1077, 1011, 880, 791 cm–1.
HRMS (ESI): m/z [M + Na]+ calcd for C35H23ClN2NaO4: 593.1239;
found: 593.1231.
1H NMR (600 MHz, DMSO-d6): δ = 8.45 (s, 1 H, OH), 8.14–8.09
(m, 3 H, HAr), 8.01–7.99 (m, 1 H, HAr), 7.40–7.37 (m, 4 H, HAr),
7.34 (s, 1 H, HAr), 7.27–7.23 (m, 6 H, HAr), 7.20–7.18 (m, 1 H, HAr),
7.14 (d, J = 7.8 Hz, 2 H, HAr), 6.99–6.94 (m, 2 H, HAr), 6.90 (d,
J = 7.8 Hz, 1 H, HAr), 6.61 (d, J = 7.8 Hz, 1 H, CH), 6.11 (d, J = 7.8
Hz, 1 H, CH), 5.69 (s, 1 H, CH), 4.83 (q, J = 16.2 Hz, 2 H, CH2),
2.33 (s, 3 H, CH3).
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 195.0, 168.9, 159.5,
143.3, 142.0, 138.1, 137.2, 136.7, 131.0, 129.1, 128.4, 128.3, 127.9,
127.2, 126.5, 125.9, 125.6, 123.6, 122.9, 122.5, 122.0, 121.9, 113.1,
108.8, 96.8, 88.5, 69.1, 63.2, 42.7, 21.3.
2′-(4-Chlorophenyl)-2′-(5-fluoro-2-oxo-1,2-dihydro-3H-indol-
3-ylidene)-Substituted 3g
Yellow solid; yield: 0.488 g (85%); mp 211–213 °C.
IR (KBr): 3087, 1744, 1708, 1654, 1556, 1465, 1333, 1274, 1240,
1187, 1149, 1093, 1002, 966, 813, 789, 750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 10.81 (s, 1 H, NH), 8.66 (s, 1
H, OH), 8.13–8.11 (m, 3 H, HAr), 7.99 (s, 1 H, HAr), 7.45 (d, J = 8.4
Hz, 2 H, HAr), 7.40 (d, J = 7.8 Hz, 1 H, HAr), 7.27–7.23 (m, 4 H,
HAr), 7.18 (d, J = 10.2 Hz, 1 H, HAr), 6.99–6.94 (m, 2 H, HAr), 6.88–
6.86 (m, 1 H, HAr), 6.67 (d, J = 7.2 Hz, 1 H, CH), 6.11 (d, J = 7.2
Hz, 1 H, CH), 5.70 (s, 1 H, CH).
HRMS (ESI): m/z [M + H]+ calcd for C42H31N2O4: 627.2278; found:
627.2275.
13C NMR (150 MHz, DMSO-d6): δ = 195.1, 194.9, 170.9, 159.7,
158.1, 156.5, 143.3, 141.9, 137.4, 137.1, 136.7, 134.8, 133.3, 130.7,
129.1, 128.6, 128.3, 128.1, 127.9, 126.7, 123.7, 123.8, 123.7, 123.0,
122.1, 114.1, 111.4, 111.2, 110.1, 108.8, 108.6, 97.7, 87.9, 68.9,
63.4.
2′-(1-Benzyl-5-chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-
2′-phenyl-Substituted 3k
Yellow solid; yield: 0.478 g (74%); mp 220–222 °C.
© Georg Thieme Verlag Stuttgart · New York
Synthesis 2014, 46, 1059–1066

1064
X.-H. Wang, C.-G. Yan
PAPER
IR (KBr): 1747, 1708, 1646, 1550, 1476, 1351, 1272, 1180, 1081,
1010, 877, 793, 747 cm–1.
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.8, 168.7, 160.5,
158.4, 156.8, 143.3, 142.0, 137.8, 137.2, 136.7, 135.3, 130.8, 129.3,
128.5, 128.4, 128.2, 128.1, 126.7, 125.9, 123.6, 123.1, 123.0, 122.9,
122.1, 114.3, 111.1, 111.0, 109.2, 108.8, 108.6, 96.0, 88.5, 69.2,
63.4, 29.4, 19.5, 13.4.
HRMS (ESI): m/z [M + Na]+ calcd for C38H29FN2NaO4: 619.2004;
found: 619.2004.
1H NMR (600 MHz, DMSO-d6): δ = 8.23 (s, 1 H, OH), 8.14–8.10
(m, 3 H, HAr), 8.01–7.99 (m, 1 H, HAr), 7.45–7.44 (m, 1 H, HAr),
7.43–7.39 (m, 4 H, HAr), 7.29–7.24 (m, 6 H, HAr), 7.21–7.17 (m, 2
H, HAr), 7.14 (d, J = 7.2 Hz, 2 H, HAr), 7.04 (d, J = 8.4 Hz, 1 H, HAr),
6.99 (t, J = 7.8 Hz, 1 H, HAr), 6.70 (d, J = 1.2 Hz, 1 H, CH), 6.13 (d,
J = 7.2 Hz, 1 H, CH), 5.77 (s, 1 H, CH), 4.86 (q, J = 15.6 Hz, 2 H,
CH2).
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.8, 168.6, 160.9,
143.3, 142.0, 137.7, 137.3, 136.8, 136.4, 130.7, 129.2, 128.6, 128.5,
128.4, 128.3, 128.0, 127.3, 126.8, 125.7, 125.5, 124.2, 123.7, 123.0,
122.1, 121.1, 110.2, 95.5, 88.6, 69.3, 63.4, 42.7.
2′-(1-Butyl-5-methyl-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-
2′-phenyl-Substituted 3o
Yellow solid; yield: 0.474 g (80%); mp 210–212 °C.
IR (KBr): 3072, 2866, 1746, 1709, 1640, 1595, 1553, 1490, 1443,
1422, 1385, 1359, 1273, 1205, 1142, 1119, 1075, 999, 877, 792,
750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.49 (s, 1 H, OH), 8.13–8.09
(m, 3 H, HAr), 8.00–7.98 (m, 1 H, HAr), 7.38–7.34 (m, 5 H, HAr),
7.25–7.21 (m, 4 H, HAr), 7.02–6.95 (m, 3 H, HAr), 6.61 (d, J = 7.8
Hz, 1 H, CH), 6.10 (d, J = 7.8 Hz, 1 H, CH), 5.64 (s, 1 H, CH), 3.58
(t, J = 7.8 Hz, 2 H, CH2), 2.35 (s, 3 H, CH3), 1.46–1.40 (m, 2 H,
CH2), 1.18 (q, J = 7.8 Hz, 2 H, CH2), 0.80 (t, J = 7.2 Hz, 3 H, CH3).
13C NMR (150 MHz, DMSO-d6): δ = 195.5, 195.0, 168.7, 159.2,
143.2, 141.9, 138.1, 137.3, 137.0, 131.2, 129.9, 128.6, 128.5, 128.3,
127.9, 126.5, 123.6, 122.9, 122.5, 122.0, 121.8, 113.0, 97.1, 88.4,
69.0, 63.2, 29.4, 21.3, 19.5, 13.5.
HRMS (ESI): m/z [M + Na]+ calcd for C41H27ClN2NaO4: 669.1552;
found: 669.1543.
2′-(1-Benzyl-5-fluoro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-
2′-phenyl-Substituted 3l
Yellow solid; yield: 0.460 g (73%); mp 211–213 °C.
IR (KBr): 3064, 1746, 1709, 1639, 1594, 1534, 1483, 1449, 1423,
1356, 1268, 1174, 1079, 1011, 955, 882, 795 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.31 (s, 1 H, OH), 8.14–8.10
(m, 3 H, HAr), 8.00–7.99 (m, 1 H, HAr), 7.41–7.39 (m, 4 H, HAr),
7.31–7.27 (m, 4 H, HAr), 7.25 (d, J = 7.2 Hz, 3 H, HAr), 7.23–7.21
(m, 1 H, HAr), 7.16 (d, J = 7.8 Hz, 2 H, HAr), 7.03–6.99 (m, 3 H,
HAr), 6.70 (d, J = 7.2 Hz, 1 H, CH), 6.13 (d, J = 7.8 Hz, 1 H, CH),
5.74 (s, 1 H, CH), 4.86 (q, J = 15.6 Hz, 2 H, CH2).
13C NMR (150 MHz, DMSO-d6): δ = 195.3, 194.8, 168.8, 160.8,
156.9, 143.3, 142.0, 137.8, 137.3, 136.7, 136.5, 134.9, 130.7, 129.2,
128.6, 128.5, 128.4, 128. 2, 128.0, 127.3, 126.8, 125.9, 123.7,
123.0, 122.1, 114.4, 111.1, 109.6, 108.8, 108.6, 96.2, 88.6, 69.2,
63.4, 42.7.
HRMS (ESI): m/z [M + H]+ calcd for C39H33N2O4: 593.2435; found:
593.2433.
2′-(1-Butyl-5-chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-
phenyl-Substituted 3p
Yellow solid; yield: 0.490 g (80%); mp 218–220 °C.
IR (KBr): 3075, 2929, 2869, 1748, 1710, 1640, 1544, 1477, 1426,
1384, 1354, 1272, 1206, 1142, 1117, 1000, 875, 794, 744 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.24 (s, 1 H, OH), 8.13–8.11
(m, 3 H, HAr), 7.99 (s, 1 H, HAr), 7.44–7.38 (m, 5 H, HAr), 7.27–7.24
(m, 5 H, HAr), 7.14 (d, J = 8.4 Hz, 1 H, HAr), 7.00–6.98 (m, 1 H,
HAr), 6.69 (d, J = 7.8 Hz, 1 H, CH), 6.12 (d, J = 7.8 Hz, 1 H, CH),
5.71 (s, 1 H, CH), 3.63–3.60 (m, 2 H, CH2), 1.46–1.40 (m, 2 H,
CH2), 1.18 (q, J = 7.2 Hz, 2 H, CH2), 0.80 (t, J = 7.2 Hz, 3 H, CH3).
HRMS (ESI): m/z [M + Na]+ calcd for C41H27FN2NaO4: 653.1847;
found: 653.1842.
2′-(1-Benzyl-5-fluoro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-
2′-(4-chlorophenyl)-Substituted 3m
Yellow solid; yield: 0.478 g (72%); mp 224–226 °C.
IR (KBr): 3071, 1747, 1712, 1638, 1537, 1483, 1345, 1269, 1175,
1093, 1010, 955, 885, 797, 750 cm–1.
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.7, 168.5, 160.6,
143.2, 142.0, 137.7, 137.3, 136.7, 130.8, 129.2, 128.6, 128.4, 128.2,
128.1, 126.7, 125.9, 125.2, 124.4, 123.6, 122.9, 122.1, 121.1, 114.2,
109.9, 95.8, 88.5, 69.2, 63.4, 29.4, 19.5, 13.4.
HRMS (ESI): m/z [M + H]+ calcd for C38H30ClN2O4: 613.1889;
found: 613.1883.
1H NMR (600 MHz, DMSO-d6): δ = 8.41 (s, 1 H, OH), 8.15–8.10
(m, 3 H, HAr), 8.01–7.99 (m, 1 H, HAr), 7.46 (d, J = 8.4 Hz, 2 H,
HAr), 7.40 (d, J = 7.2 Hz, 1 H, HAr), 7.30–7.20 (m, 7 H, HAr), 7.15
(d, J = 7.2 Hz, 2 H, HAr), 7.03–6.97 (m, 3 H, HAr), 6.68 (d, J = 7.2
Hz, 1 H, CH), 6.13 (d, J = 7.2 Hz, 1 H, CH), 5.79 (s, 1 H, CH), 5.77
(s, 1 H, CH), 4.86 (q, J = 15.6 Hz, 2 H, CH2).
13C NMR (150 MHz, DMSO-d6): δ = 195.1, 195.0, 168.8, 160.1,
157.0, 143.3, 141.9, 137.4, 137.0, 136.8, 136.4, 134.9, 133.3, 130.6,
129.1, 128.6, 128.5, 128.4, 128.3, 127.9, 127.8, 127.3, 126.8, 123.8,
123.1, 123.0, 122.1, 114.4, 111.2, 96.3, 88.0, 69.1, 63.4, 56.0. 42.8.
2′-(1-Butyl-5-fluoro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-
(4-chlorophenyl)-Substituted 3q
Yellow solid; yield: 0.460 g (73%); mp 222–224 °C.
IR (KBr): 3078, 2953, 2870, 1749, 1712, 1642, 1593, 1547, 1484,
1459, 1424, 1355, 1271, 1185, 1144, 1094, 1003, 954, 875, 795,
750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.43 (s, 1 H, OH), 8.14–8.10
(m, 3 H, HAr), 7.99–7.98 (m, 1 H, HAr), 7.45 (d, J = 9.0 Hz, 2 H,
HAr), 7.41 (d, J = 7.8 Hz, 1 H, HAr), 7.28–7.22 (m, 5 H, HAr), 7.12–
7.10 (m, 1 H, HAr), 7.06–7.02 (m, 1 H, HAr), 6.98 (t, J = 7.5 Hz, 1 H,
HAr), 6.67 (d, J = 7.8 Hz, 1 H, CH), 6.12 (d, J = 7.8 Hz, 1 H, CH),
5.73 (s, 1 H, CH), 3.65–3.60 (m, 2 H, CH2), 1.47–1.41 (m, 2 H,
CH2), 1.21–1.15 (m, 2 H, CH2), 0.80 (t, J = 7.3 Hz, 3 H, CH3).
13C NMR (150 MHz, DMSO-d6): δ = 195.2, 194.9, 168.6, 159.8,
158.4, 156.8, 143.2, 141.9, 137.4, 137.0, 136.8, 135.3, 133.3, 130.7,
129.1, 128.6, 128.4, 128.2, 128.0, 127.9, 126.8, 123.8, 123.0, 122.9,
122.1, 114.3, 111.3, 111.1, 109.3, 108.7, 96.5, 87.9, 68.9, 63.4,
29.4, 19.5, 13.5.
HRMS (ESI): m/z [M + Na]+ calcd for C41H26ClFN2NaO4:
687.1457; found: 687.1450.
2′-(1-Butyl-5-fluoro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)-2′-
phenyl-Substituted 3n
Yellow solid; yield: 0.465 g (78%); mp 217–219 °C.
IR (KBr): 3084, 2869, 1749, 1711, 1638, 1541, 1483, 1456, 1382,
1356, 1270, 1186, 1143, 1104, 1004, 953, 874, 796 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.35 (s, 1 H, OH), 8.14–8.10
(m, 3 H, HAr), 8.00–7.99 (m, 1 H, HAr), 7.42–7.37 (m, 4 H, HAr),
7.28–7.22 (m, 5 H, HAr), 7.12–7.10 (m, 1 H, HAr), 7.06–7.03 (m, 1
H, HAr), 6.98 (t, J = 7.8 Hz, 1 H, HAr), 6.70 (d, J = 7.8 Hz, 1 H, CH),
6.11 (d, J = 7.8 Hz, 1 H, CH), 5.69 (s, 1 H, CH), 3.65–3.57 (m, 2 H,
CH2), 1.45–1.40 (m, 2 H, CH2), 1.19 (q, J = 7.2 Hz, 2 H, CH2), 0.80
(t, J = 7.2 Hz, 3 H, CH3).
HRMS (ESI): m/z [M + H]+ calcd for C38H29ClFN2O4: 631.1794;
found: 631.1787.
Synthesis 2014, 46, 1059–1066
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Spiro[indane-2,1′-pyrrolo[2,1-a]isoquinolines]
1065
2′-[2-Oxoacenaphthen-1(2H)-ylidene]-2′,3′-dihydro-10b′H-spi-
ro[indene-2,1′-pyrrolo[2,1-a]isoquinoline]-1,3-diones 4a,b via
Domino Three-Component Reaction; General Procedure
A mixture of isoquinoline (1.2 mmol) and phenacyl bromide (1.0
mmol) in EtOH (10.0 mL) was stirred at r.t. for ~1 h. Then acenaph-
thenequinone (1.0 mmol), indane-1,3-dione (1.0 mmol), and Et3N
(0.5 mmol) were added. The mixture was heated at 50 °C for over-
night. After cooling, the resulting precipitate was collected by filtra-
tion, and this was recrystallized (EtOH–CHCl3) to give the pure
product for analysis.
References
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He, X. W. Tetrahedron Lett. 2009, 50, 6981.
2′-Phenyl-Substituted 4a
Yellow solid; yield: 0.428 g (67%); mp 214–216 °C.
IR (KBr): 3058, 1745, 1708, 1648, 1618, 1520, 1462, 1414, 1347,
1271, 1224, 1151, 1088, 1014, 974, 871, 774 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.19 (d, J = 7.8 Hz, 1 H, HAr),
8.14 (br s, 1 H, HAr), 8.11 (s, 2 H, HAr), 8.01 (s, 1 H, HAr), 7.83 (d,
J = 7.2 Hz, 1 H, HAr), 7.77 (d, J = 5.4 Hz, 1 H, HAr), 7.71–7.69 (m,
3 H, HAr), 7.45 (d, J = 6.6 Hz, 1 H, HAr), 7.40 (br s, 4 H, HAr), 7.35
(br s, 3 H, HAr), 7.27–7.25 (m, 1 H, HAr), 7.00–6.98 (m, 1 H, HAr),
6.65 (d, J = 6.0 Hz, 1 H, CH), 6.12 (d, J = 6.6 Hz, 1 H, CH), 5.70 (s,
1 H, CH).
13C NMR (150 MHz, DMSO-d6): δ = 195.4, 194.9, 192.7, 159.6,
143.3, 142.0, 137.8, 137.3, 136.7, 134.9, 134.0, 133.4, 131.8, 131.0,
129.6, 128.7, 128.6, 128.5, 128.4, 128.0, 127.9, 126.5, 126.0, 123.7,
123.1, 123.0, 122.1, 122.0, 120.2, 113.8, 105.7, 88.7, 69.0, 63.4.
(b) Muthusaravanan, S.; Perumal, S.; Yogeeswari, P.;
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Tetrahedron 2013, 69, 5016. (f) Paira, R.; Mondal, S.;
Chowdhury, A.; Banerjee, M.; Maity, A.; Hazra, A.;
Mondal, N. B. Tetrahedron Lett. 2013, 54, 3046.
HRMS (ESI): m/z [M + Na]+ calcd for C38H23NNaO4: 580.1519;
found: 580.1512.
2′-(4-Chlorophenyl)-Substituted 4b
Yellow solid; yield: 0.425 g (72%); mp 204–206 °C.
IR (KBr): 3068, 2831, 1748, 1711, 1653, 1616, 1541, 1489, 1460,
1417, 1345, 1271, 1224, 1152, 1087, 1011, 970, 932, 872, 828, 778,
750 cm–1.
1H NMR (600 MHz, DMSO-d6): δ = 8.20 (d, J = 7.8 Hz, 1 H, HAr),
8.17–8.15 (m, 1 H, HAr), 8.13–8.10 (m, 2 H, HAr), 8.01–8.0 (m, 1 H,
HAr), 7.85–7.84 (m, 1 H, HAr), 7.78 (d, J = 6.6 Hz, 1 H, HAr), 7.73
(d, J = 7.8 Hz, 1 H, HAr), 7.71–7.69 (m, 2 H, HAr), 7.59 (s, 1 H, HAr),
7.47 (d, J = 8.4 Hz, 2 H, HAr), 7.43 (d, J = 7.2 Hz, 1 H, HAr), 7.40
(d, J = 7.2 Hz, 1 H, HAr), 7.36 (d, J = 8.4 Hz, 2 H, HAr), 7.27 (t,
J = 7.5 Hz, 1 H, HAr), 6.99 (t, J = 7.6 Hz, 1 H, HAr), 6.65 (d, J = 7.8
Hz, 1 H, CH), 6.13 (d, J = 7.8 Hz, 1 H, CH), 5.72 (s, 1 H, CH).
13C NMR (100 MHz, DMSO-d6): δ = 195.6, 195.4, 193.2, 159.4,
143.7, 142.3, 137.9, 137.5, 137.3, 135.4, 134.4, 133.8, 132.4, 131.4,
130.1, 129.6, 129.0, 128.9, 128.5, 128.4, 127.1, 124.2, 123.6, 123.5,
122.5, 120.7, 114.3, 106.2, 88.7, 69.3, 63.8.
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Acknowledgment
This work was financially supported by the National Natural Sci-
ence Foundation of China (Grant No. 21172189) and the Priority
Academic Program Development of Jiangsu Higher Education In-
stitutions. We also thanked Analysis and Test Center of Yangzhou
University for providing necessary instruments for analysis.
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Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.SnuIomprifgtooatrinSugpIoi
nnfomartit
© Georg Thieme Verlag Stuttgart · New York
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