Copper(II)-catalyzed tandem synthesis of substituted 3-methyleneisoindolin- 1-ones

Article abstract of DOI:10.1002/cjoc.201300346

An efficient strategy for the synthesis of a variety of 3-methyleneisoindolin-1-ones has been developed. The reaction proceeded from coupling of 2-iodobenzamides (or 2-bromobenzamides) and terminal alkynes via Cu(OAc)₂·H₂O/2,2′-biimi

Full text of DOI:10.1002/cjoc.201300346

FULL PAPER
DOI: 10.1002/cjoc.201300346
Copper(II)-Catalyzed Tandem Synthesis of Substituted
3-Methyleneisoindolin-1-ones
Jie Pan, Zhen Xu, Runsheng Zeng,* and Jianping Zou
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and
Materials Science, Soochow University, Suzhou, Jiangsu 215123, China
An efficient strategy for the synthesis of a variety of 3-methyleneisoindolin-1-ones has been developed. The re-
action proceeded from coupling of 2-iodobenzamides (or 2-bromobenzamides) and terminal alkynes via
Cu(OAc)2•H2O/2,2'-biimidazole catalyzed in DMF at 60 ℃ and subsequent additive cyclization produced substi-
tuted 3-methyleneisoindolin-1-ones in good to excellent yields.
Keywords 3-methyleneisoindolin-1-ones, Cu(OAc)2•H2O, 2,2'-biimidazole, additive cyclization
Introduction
Cu(OAc)2•H2O/2,2'-biimidazole.
The 3-methyleneisoindolin-1-one is a core structure
of numerous natural products or designed pharmaceuti-
cal molecules,[1] which have attracted much attention
due to their unique biological activities, such as anti-
cancer activity, antibacterial activity, etc. For example,
compound 1, an alkaloid containing the isoindolinone
moiety, isolated from a Saccharothrise sp. has anti-
microbial, hypotensive and cytotoxic activities.[2] Com-
pound 2 exhibited sedative activity[1h] (Figure 1). Con-
siderable efforts have been directed toward the synthesis
of 3-methyleneisoindolin-1-ones.
O
H
Me
Me
N
O
N
N
F
O
N
O
N
H
Me
MeO
N
NHMe
Me
1
2
Figure 1 The structure of compound 1 and compound 2.
3-Methyleneisoindolin-1-ones have been prepared
via using phthalimides as starting materials, which un-
dergo Wittig reaction[3] or addition of organometallic
reagents and subsequent dehydration[4] to give the target
molecules, as well as Grignard[5] or lithiation[6] or mis-
call-aneous[7,8] procedures, Diels-Alder reactions,[9] re-
arrangement reactions,[10] and photochemical reac-
tions.[11] The reduction of N-substituted phthalimides[12]
and the condensation of phthalaldehyde[13] also afford
3-methyleneisoindolin-1-ones. Besides the above clas-
sical methods, efficient methods for the synthesis of
various 3-methyleneisoindolin-1-ones catalyzed by
metal complexes have been reported. Cobalt and rho-
dium carbonyl complexes can be used as the catalysts to
synthesize 3-methyleneisoindolin-1-ones.[14] Several
examples of palladium catalysis have appeared.[15-19] But
copper-catalyzed syntheses of 3-methyleneisoindolin-1-
ones were rare.[20] Herein, we wish to report a direct and
efficient approach to 3-methyleneisoindolin-1-ones
through the coupling reaction of 2-iodobenzamides (or
2-bromobenzamides) and terminal alkynes catalyzed by
Results and Discussion
Initially, the reaction between N-phenyl-2-iodoben-
zamide (3a) and phenylacetylene (4a) was selected as a
model reaction to screen the optimal reaction conditions
(Table 1). We explored the effects of the solvent. The
results revealed that the use of DMF as solvent achieved
the best result with K2CO3 as base under argon at 60 ℃
for 24 h in the presence of Cu(OAc)2•H2O/2,2'-biimid-
azole, achieving the desired product 5a in 88% yield
(Table 1, Entry 4). Similar result was observed when the
solvent was changed to DMSO (Table 1, Entry 1).
However, poor yields were obtained if the reaction was
carried out in i-PrOH (Table 1, Entry 2) and the fact that
no desired product was isolated in the presence of tolu-
ene (Table 1, Entry 3). Next, the base was further inves-
tigated. Switching base to Cs2CO3 and K3PO4 had little
influence to this reaction (Table 1, Entries 5 and 6). Re-
placing K2CO3 with KOH (Table 1, Entry 8) resulted in
poorer yields, whereas no reaction was observed in NEt3
*
E-mail: zengrunsheng@suda.edu.cn
Received April 24, 2013; accepted May 29, 2013; published online July 5, 2013.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201300346 or from the author.
1022
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Chin. J. Chem. 2013, 31, 1022—1026

Copper(II)-Catalyzed Tandem Synthesis of Substituted 3-Methyleneisoindolin-1-ones
(Table 1, Entry 7). Then, the influences of temperature
and time on the reaction were examined. The yield un-
changed when temperature decreased to 80 ℃ or 60
℃ from 100 ℃ (Table 1, Entries 10 and 11). However,
a moderate yield was produced at 40 ℃ (Table 1, En-
try 13). The yield was decreased to some extent when
the reaction was carried out at the elevated temperature
(Table 1, Entry 9). Extending the time to 48 h did not
improve yield (Table 1, Entry 14). An 80% yield was
produced in the absence of argon (Table 1, Entry 12).
tained when the catalyst was changed to CuI or CuSO4•
5H2O or CuCl2•H2O (Table 2, Entries 8－10), whereas
no reaction was observed in FeCl3•6H2O (Table 2, Entry
11). Based on these results, we chose Cu(OAc)2•H2O as
the catalyst, L1 as the ligand, K2CO3 as the base, and
DMF as the solvent under argon in the subsequent stud-
ies.
H
N
H
N
N
N
N
N
N
N
Table 1 Coupling of N-phenyl-2-iodobenzamide with phenyl-
acetylene under different conditionsa
L1
L2
O
.
Cu(OAc)2 H2O, ligand
N
N
N
N
+
N
base, solvent
H
L3
L4
I
4a
Figure 2 Ligands used in the study.
3a
O
Table 2 Coupling of N-phenyl-2-iodobenzamide with phenyl-
acetylene under different conditionsa
N
O
Cu salt, ligand L
+
N
5a
K2CO3, DMF, 48 h, 60 oC
H
I
Entry Base
Solvent Temp (℃)/Time (h) Yieldb%
4a
3a
1
2
K2CO3
DMSO
i-PrOH
toluene
DMF
DMF0
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
100/24
100/24
100/24
100/24
100/24
100/24
100/24
100/24
120/24
80/24
82
15
O
K2CO3
K2CO3
K2CO3
Cs2CO3
K3PO4
Et3N
N
3
trace
88
4
5
75
5a
Entry
Catalyst
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
Cu(OAc)2•H2O
CuI
Ligand Cu∶L (mmol%) Yieldb/%
6
82
7
trace
55
1
2
3
4
5
6
7
8
9
L1
L2
L3
L4
No
L1
L1
L1
L1
L1
L1
20∶10
20∶10
20∶10
20∶10
20∶10
40∶20
10∶5
88
73
68
67
70
88
82
75
78
78
NR
8
KOH
9
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
83
10
11
12c
13
14
88
60/24
88
60/24
80
40/24
62
60/48
88
20∶10
20∶10
20∶10
20∶10
a
All reactions were carried out using 1.0 mmol N-phenyl-2-
CuSO4•5H2O
iodobenzamide (3a), 1.2 mmol phenylacetylene (4a), 2.0 mmol
base, 0.2 mmol Cu(OAc)2•H2O, 0.1 mmol 2,2'-biimidazole and 2
mL solvent. b Isolated yield. c The reaction was carried out in the
air.
10 CuCl2•H2O
11 FeCl3•6H2O
a All reactions were carried out using 1.0 mmol N-phenyl-2-iodo-
benzamide (3a), 1.2 mmol phenylacetylene (4a), 2.0 mmol
K2CO3, Cu catalyst, ligand L and 2 mL DMF under 60 ℃, 48 h,
in argon. b Isolated yield.
Finally, we optimized the catalyst, ligands and their
loading. The results are summarized in Table 2. As evi-
dent from the satisfactory yields that were observed
when L1, L2, L3, L4 (Figure 2) and no ligand were
used (Table 2, Entries 1－5), but L1 gave the highest
product yield of 88%. 20 mol% Cu(OAc)2•H2O and 10
mol% L1 were found to be sufficient to promote the
reaction and increased amounts of the catalyst and
ligand did not lead to any changes in the reaction yield
(Table 2, Entries 1, 6 and 7). Moderate yields were ob-
With the optimal conditions in hand, we explored the
scope of substrates (Table 3). A wide range of N-sub-
stituents were tolerated, including benzyl, allyl, phenyl,
proton, and alkyl groups, systems bearing electron-do-
nating and electron-withdrawing substituents performed
well (Table 3, Entries 1－13 and 16). Some functional-
ized arylacetylenes also worked well, giving the corre-
Chin. J. Chem. 2013, 31, 1022—1026
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1023

Pan et al.
FULL PAPER
sponding products in good yields (Table 3, Entries 14
and 15). This reaction was also effective with 2-bromo-
benzamides, but higher temperature (100 ℃) was re-
quired (Table 3, Entries 17－21). Furthermore, this
one-pot reaction was highly stereoselective, and gave
the Z-isomer as the main product.
Table 4 Copper-catalyzed tandem synthesis of substituted
3-methyleneisoindolin-1-onea
.
Cu(OAc)2 H2O (20 mol%)
2,2'-biimidazole (10 mol%)
K2CO3 (2 equiv.), DMF
O
Ph
N
+
R
R
R2
H
Y
X
4
60 oC, 24 h, X = I, Br
3
Ph
Ph
Table 3 Copper-catalyzed tandem synthesis of substituted
3-methyleneisoindolin-1-onea
N
.
Y
Cu(OAc)2 H2O (20 mol%)
O
X
5
2,2'-biimidazole (10 mol%)
H
Product Yieldb/%
+
R2
N
Entry
X
I
Y
C
C
C
N
R
5-Me
4-Cl
4-Cl
H
R1
K2CO3 (2 equiv.), DMF
60 oC, 24 h, X = I, Br
4
O
3
1
2
3
4
5q
5r
5r
5s
90
94
80
49
I
R2
Br
Br
N
R1
a All reactions were carried out using 1.0 mmol N-substituted-
2-iodobenzamide (3), 1.2 mmol phenylacetylene (4a), 2.0 mmol
K2CO3, 0.2 mmol Cu(OAc)2•H2O, 0.1 mmol ligand L1 and 2 mL
DMF under 60 ℃, 24 h, in argon. b Isolated yield.
O
5
Entry
1
X
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
R1
R2
Product Yieldb/%
Ph
Ph
5a
5b
5c
5d
5e
5f
89
89
88
95
94
92
84
90
77
54
95
87
98
90
86
98
82
88
90
85
87
2
Bn
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
(Scheme 1). We envisaged that coupling of 3a with 4a
afforded A by Sonogashira reaction, then A might un-
dergo deprotonation of the amide moiety and subse-
quent addition to C－C triple bond under the action of
the copper complex (as intermediate B) to afford inter-
mediate C, then protonation of this intermediate af-
forded copper salt and released the product 5a. Single
crystal X-ray analysis conclusively confirmed the struc-
ture of the isolated (Z)-3-benzylidene-2-(4-chlorophe-
nyl)isoindolin-1-one (5e) and an ORTEP diagram of 5e
was shown in Figure 3. This result indicated that the
Cu(OAc)2•H2O-mediated additive cyclization of the
amide moiety to the triple bond took place in a 5-exo
manner exclusively, which is different with base or
Lewis acid-mediated additive cyclization (both 5-exo
and 6-endo attacks were observed).[15f]
3
2-ClC6H4
3-ClC6H4
4-ClC6H4
2-MeC6H4
4-MeC6H4
4-MeOC6H4
n-C4H9
4
5
6
7
5g
5h
5i
8
9
10
11
12
13
14
15
16
17c
18c
19c
20c
21c
n-C6H13
5j
4-OCH2PhPh Ph
1-naphthyl Ph
2,6-Me2C6H4 Ph
5k
5l
5m
Ph
Ph
H
4-MeOC6H4 5n
4-EtC6H4
5o
5p
5a
5d
5e
5f
Ph
Ph
Ph
Ph
Ph
Ph
Br Ph
Br 3-ClC6H4
Br 4-ClC6H4
Br 2-MeC6H4
Br 4-MeOC6H4
5h
a All reactions were carried out using 1.0 mmol N-substituted-
2-iodobenzamide (3), 1.2 mmol arylacetylenes (4), 2.0 mmol
K2CO3, 0.2 mmol Cu(OAc)2•H2O, 0.1 mmol ligand L1 and 2 mL
DMF under 60 ℃, 24 h, in argon. b Isolated yield. c The reaction
was carried out in DMF at 100 ℃.
Figure 3 ORTEP diagram of 5e.
Notably, N-phenyl-2-iodobenzamide and N-phenyl-
2-bromobenzamide with various substituents provided
high yields of desired products (Table 4, Entries 1－3).
However, N-phenyl-2-bromo-nicotinamide provided
only a moderate yield (Table 4, Entry 4).
Conclusions
In conclusion, we have developed a simple and rapid
Cu(OAc)2•H2O/2,2'-biimidazole catalyzed coupling/ad-
dative cyclization domino reaction process for the con-
struction of substituted 3-methyleneisoindolin-1-ones in
On the basis of the above results, we proposed the
following reaction mechanism for this cascade sequence
1024
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Chin. J. Chem. 2013, 31, 1022—1026

Copper(II)-Catalyzed Tandem Synthesis of Substituted 3-Methyleneisoindolin-1-ones
Scheme 1 Tentative mechanism for domino reaction catalyzed by copper(II)
CuL2, base
O
O
CuL2
N
H
N
-
O
I
N
H
L2Cu
A
CuL2
B
3a
O
base
H2O
N
H2O
CuL2
L2Cu
6-endo
5-exo
C
addition
X
4a
addition
O
N
N
O
Cl
5a
good to excellent yields from various 2-halobenzamides
7.08 (s, 5H), 6.83－6.97 (m, 6H); 13C NMR (100 MHz,
CDCl3) δ: 168.4, 139.0, 136.3, 134.7, 133.9, 132.8,
129.6, 129.5, 128.6, 128.2, 127.6, 127.1, 127.0, 124.7,
and terminal alkynes. Considering the relatively inex-
pensive catalytic system and the commercial availability
of the starting materials, it should be of great benefit for
organic synthesis.
119.6, 108.7; HRMS calcd for C21H15NO (M ＋
297.1154, found 297.1154.
)
(Z)-3-Benzylidene-2-(4-chlorophenyl)isoindolin-1-
one (5e)[23] White solid, m.p. 142－144 ℃; 1H NMR
(400 MHz, CDCl3) δ: 7.95 (d, J＝7.6 Hz, 1H), 7.86 (d,
J＝7.8 Hz, 1H), 7.69 (t, J＝7.5 Hz, 1H), 7.56 (t, J＝7.4
Hz, 1H), 7.10－6.92 (m, 7H), 6.87 (d, J＝7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ: 168.0, 138.7, 134.6,
134.4, 133.5, 132.9, 132.8, 129.6, 129.4, 128.6, 128.4,
127.8, 127.6, 127.1, 124.2, 119.7, 108.0; HRMS calcd
for C21H14ClNO (M＋) 331.0764, found 331.0764.
Experimental
General
Column chromatograph was performed with silica
gel (300－400 mesh) and analytical TLC on silica
60-F254. 1H NMR spectra were measured on an
Inova-400 MHz spectrometer in CDCl3 (100 MHz, 13C
NMR) with chemical shift (δ) relative to TMS as inter-
nal standard. HRMS was determined by using micro-
mass OA-TOF instrument. All of the reagents were used
directly as obtained commercially. Some alkynes were
prepared according to literature methods,[21,22] purified
by chromatography.
(Z)-3-Benzylidene-2-butylisoindolin-1-one (5i)[20]
Colorless liquid; 1H NMR (400 MHz, CDCl3) δ: 7.83 (d,
J＝7.5 Hz, 1H), 7.38－7.45 (m, 6H), 7.28－7.29 (m,
2H), 6.54 (s, 1H), 3.89 (t, J＝7.4 Hz, 2H), 1.70－1.77
(m, 2H), 1.40－1.48 (m, 2H), 0.99 (t, J＝7.3 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ: 167.6, 137.3, 133.9,
130.7, 128.5, 128.4, 127.9, 127.6, 127.0, 126.5, 122.1,
118.2, 105.5, 40.1, 29.2, 18.6, 12.4; HRMS calcd for
C19H19NO (M＋) 277.1467, found 277.1466.
General procedure for the synthesis of substituted
3-methyleneisoindolin-1-ones
A sealed tube was charged with a magnetic stirrer
and 2-iodobenzamide (1.0 mmol), phenylacetylene (1.2
mmol), Cu(OAc)2•H2O (0.2 mmol), 2,2'-biimidazole
(0.1 mmol), K2CO3 (2.0 mmol), DMF (2.0 mL). The
reaction mixture was stirred under argon at 60 ℃ for
24 h. After cooling to room temperature, the reaction
mixture was diluted with water and extracted with ethyl
acetate. The organic layer was dried over anhydrous
sodium sulfate and evaporated under reduced pressure.
The crude product was purified by chromatography on
silica gel using ethyl acetate/petroleum ether as eluent to
afford substituted 3-methyleneisoindolin-1-ones.
(Z)-3-Benzylidene-2-(4-(benzyloxy)phenyl)isoindo-
1
lin-1-one (5k) Yellow solid, m.p. 124－126 ℃; H
NMR (400 MHz, CDCl3) δ: 7.93－7.95 (m, 1H), 7.83－
7.86 (m, 1H), 7.64－7.67 (m, 1H), 7.54－7.57 (m, 1H),
7.31－7.38 (m, 5H), 6.70－6.93 (m, 10H), 4.98 (s, 2H);
13C NMR (100 MHz, CDCl3) δ: 168.7, 158.9, 139.0,
137.4, 135.1, 134.1, 132.8, 129.6, 129.4, 129.0, 128.7,
128.4, 128.3, 127.6, 127.4, 126.1, 124.2, 120.1, 115.2,
＋
108.0, 70.5; HRMS calcd for C28H21NO2 (M
403.1572, found 403.1572.
)
(Z)-3-Benzylidene-2-phenylisoindolin-1-one (5a)[15f]
White solid, m.p. 197－198 ℃; H NMR (400 MHz,
(Z)-3-Benzylidene-2-(2,6-dimethylphenyl)isoindo-
1
lin-1-one (5m)[24] White solid, m.p. 115－116 ℃; H
1
NMR (400 MHz, CDCl3) δ: 7.97 (d, J＝7.5 Hz, 1H),
7.86 (d, J＝7.7 Hz, 1H), 7.69 (t, J＝7.1 Hz, 1H), 7.56 (t,
CDCl3) δ: 7.96 (d, J＝7.5 Hz, 1H), 7.87 (d, J＝7.8 Hz,
1H), 7.68 (t, J＝7.2 Hz, 1H), 7.55 (t, J＝7.4 Hz, 1H),
Chin. J. Chem. 2013, 31, 1022—1026
© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1025

Pan et al.
FULL PAPER
J＝7.5 Hz, 1H), 6.70－6.99 (m, 9H), 2.05 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ: 167.7, 139.0, 136.4, 134.9,
133.9, 133.2, 132.6, 129.6, 128.8, 128.5, 128.4, 127.8,
126.7, 124.2, 120.1, 108.1, 18.6; HRMS calcd for
C23H19NO (M＋) 325.1467, found 325.1468.
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(Z)-3-(4-Ethylbenzylidene)-2-phenylisoindolin-1-
1
one (5o) White solid, m.p. 130－132 ℃; H NMR
(400 MHz, CDCl3) δ: 7.95 (d, J＝7.4 Hz, 1H), 7.85 (d,
J＝7.6 Hz, 1H), 7.67 (t, J＝7.6 Hz, 1H), 7.54 (t, J＝7.4
Hz, 1H), 7.07 (s, 5H), 6.82 (s, 1H), 6.72－6.78 (m, 4H),
2.45－2.50 (m, 2H), 1.11 (t, J＝7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ: 168.2, 143.9, 138.1, 136.3, 134.2,
132.9, 131.6, 129.7, 129.3, 128.9, 127.6, 127.3, 126.6,
126.2, 124.1, 119.2, 108.0, 28.8, 16.7; HRMS calcd for
C23H19NO (M＋) 325.1467, found 325.1466.
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(Z)-3-Benzylidene-6-methyl-2-phenylisoindolin-1-
1
one (5q) White solid, m.p. 179－180 ℃; H NMR
(300 MHz, DMSO-d6) δ: 8.01 (d, J＝7.6 Hz, 1H), 7.63
(s, 1H), 7.57 (d, J＝7.2 Hz, 1H), 7.08 (s, 5H), 7.00 (s,
1H), 6.77－6.94 (m, 5H), 2.47 (s, 3H); 13C NMR (75
MHz, DMSO-d6) δ: 167.85, 140.15, 136.84, 136.72,
134.50, 134.31, 129.73, 128.63, 127.94, 127.71, 127.20,
127.00, 123.76, 120.79, 107.96, 21.71; HRMS calcd for
C22H17NO (M＋) 311.1310, found 311.1215.
[7] Rowe, F. M.; McFadyen, W. T.; Peters, A. T. J. Chem. Soc. 1947, 468.
[8] (a) Pojer, P. M.; Ritchie, E.; Taylor, W. C. Aust. J. Chem. 1968, 21, 1375;
(b) Camilleri, P.; Cassola, A. J. Chem. Soc., Chem. Commun. 1978, 807;
(c) Rowe, R. K.; Shelton, B. R. J. Org. Chem. 1990, 55, 4603; (d) Ta-
keuchi, H.; Eguchi, S. J. Chem. Soc., Perkin Trans. 1989, 2149.
[9] (a) Taylor, E. C.; Zhou, P.; Jenning, L. D.; Mao, Z.; Hu, B.; Jun, J. G.
Tetrahedron Lett. 1997, 38, 521; (b) Gutierrez, A. J.; Shea, K. J.;
Svoboda, J. J. J. Org. Chem. 1989, 54, 4335.
(Z)-3-Benzylidene-5-chloro-2-phenylisoindolin-1-
1
one (5r) Pale green solid, m.p. 177－178 ℃; H
[10] Guillaumel, J.; Boccara, N.; Demersemann, P.; Royer, R. J. Chem. Soc.,
Chem. Commun. 1988, 1604.
NMR (400 MHz, CDCl3) δ: 7.88 (d, J＝8.1 Hz, 1H),
7.82 (s, 1H), 7.51 (dd, J＝8.1, 1.2 Hz, 1H), 7.14－7.04
(m, 5H), 7.00 (t, J＝7.2 Hz, 1H), 6.93 (t, J＝7.5 Hz,
2H), 6.85 (d, J＝7.5 Hz, 2H), 6.80 (s, 1H); 13C NMR
(101 MHz, CDCl3) δ: 165.42, 138.59, 137.35, 134.03,
131.66, 131.52, 128.04, 127.57, 126.71, 125.74, 125.55,
125.36, 124.55, 123.59, 118.26, 107.30; HRMS calcd
for C21H14ClNO (M＋) 331.1764, found 331.1665.
[11] (a) Freccero, M.; Fasani, E.; Albini, A. J. Org. Chem. 1993, 58, 1740; (b)
Weidner-Wells, M. A.; Oda, K.; Mazzocchi, P. H. Tetrahedron 1997, 53,
3475.
[12] (a) Brewster, J. H.; Fusco, A. M.; Carosino, L. E.; Corman, B. G. J. Org.
Chem. 1963, 28, 498; (b) Milewska, M. J.; Bytner, T.; Polonski, T. Syn-
thesis 1996, 1485.
[13] (a) Yamamoto, I.; Tabo, Y.; Gotoh, H. Tetrahedron Lett. 1971, 2295; (b)
Dominh, T.; Johnson, A. L.; Jones, J. E.; Senise, P. P. Jr. J. Org. Chem.
1977, 42, 4217; (c) Grigg, R.; Gunaratne, H. Q. N.; Sridharan, V. J.
Chem. Soc., Chem. Commun. 1985, 1183; (d) Takahashi, I.; Kawakami,
T.; Hirano, E.; Yokota, H.; Kitajima, H. Synlett 1996, 353; (e) Takahashi,
I.; Hatanaka, M. Heterocycles 1997, 45, 2475.
(Z)-5-Benzylidene-6-phenyl-5,6-dihydropyrrolo[3,
4-b]pyridin-7-one (5s) White solid, m.p. 130－132
1
℃; H NMR (300 MHz, CDCl3) δ: 8.86 (d, J＝4.7 Hz,
1H), 8.22 (d, J＝7.7 Hz, 1H), 7.46 (dd, J＝8.4, 5.7 Hz,
2H), 7.13 (s, 5H), 6.94 (dt, J＝17.5, 7.2 Hz, 5H); 13C
NMR (75 MHz, CDCl3) δ: 165.93, 156.99, 153.95,
135.55, 133.41, 133.24, 132.23, 129.61, 128.61, 127.51,
127.33, 124.16, 121.68, 110.41; HRMS calcd for
C20H14N2O (M＋) 298.1106, found 298.1013.
[14] Wilkinson, G.; Stone, F. G. A.; Abel, E. W. Comprehensive Organometal-
lic Chemistry, 1st ed., Pergamon, Oxford, 1982, p. 1.
[15] (a) Mori, M.; Chiba, K.; Ban, Y. J. Org. Chem. 1978, 43, 1684; (b) La-
rock, R. C.; Liu, C.-L.; Lau, H. H.; Varaprath, S. Tetrahedron Lett. 1984,
25, 4459; (c) Burns, B.; Grigg, R.; Santhakumar, V.; Sridharan, V.; Ste-
venson, P.; Worakun, T. Tetrahedron 1992, 48, 7297; (e) Cho, C. S.; Ji-
ang, L. H.; Shim, S. C. Synth. Commun. 1998, 28, 849; (f) Kundu, N. G.;
Khan, M. W. Tetrahedron 2000, 56, 4777; (g) Kondo, Y.; Shiga, F.; Mu-
rata, N.; Sakamoto, T.; Yamanaka, H. Tetrahedron 1994, 50, 11803.
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[17] Khan, M. W.; Kundu, N. G. Synlett 1997, 1435.
Acknowledgement
This work was supported by the Team Innovation
Project of Suzhou University.
[18] Sarkar, S.; Dutta, S.; Dey, R.; Naskar, S. Tetrahedron Lett. 2012, 53,
6789.
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(Pan, B.; Fan, Y.)
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