DBU-catalyzed tandem additions of electron-deficient 1,3-conjugated enynes with 2-aminomalonates: A facile access to highly substituted 2-pyrrolines

Article abstract of DOI:10.1039/c2cc30840a

An efficient, metal free approach to highly substituted 2-pyrrolines by DBU-catalyzed tandem additions (a formal [3+2] cycloaddition) of electron-deficient 1,3-conjugated enynes and 2-aminomalonates under mild conditions was developed.

Full text of DOI:10.1039/c2cc30840a

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Supporting information
DBU-catalyzed cyclization of electron-deficient 1,3-conjugated enynes
with 2-aminomalonates: a facile access to highly substituted
2
,3-dihydro-1H-pyrroles
a
Xiuzhao Yu, Guanghua Zhou and Junliang Zhang*
Shanghai Key Laboratory of Green Chemistry and Chemical Processes
Department of Chemistry
East China Normal University
3
663 N. Zhongshan Road, Shanghai 200062 (P. R. China)
Fax: (+86)21-6223-5039
E-mail: jlzhang@chem.ecnu.edu.cn
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Contents:
The control experiments about the reactivity of E- and Z-isomers
S3
S3
Typical procedure for the synthesis of 2-pyrrolines 3
Synthesis of 2-pyrroline 4
S21
S22
X-ray crystal structure of 3e
1
13
H NMR and C NMR spectrum for the compounds
S23
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The control experiments about the reactivity of E- and Z-isomers:
Ph
Ph
CO2Me
CO Et
Ph
2
DBU (20 mol%)
+
Ac
EtO C
Ph
2
N
CO Et
o
Bn +
2
Ph
DMF, 40 C
N
CO Me
H
EtO C
2
2
CO Me
3
h
Ac
2
1
a (E/Z = 1.1/1)
2a
0.3 mmol
E-1a
E-isomer only
4% NMR yield
3a
5
4% NMR yield
0
.2 mmol
4
Ph
Ph
EtO C
CO2Me
Bn +
CO Et
Ph
2
DBU (20 mol%)
+
Ac
Ph
2
N
CO Et
o
2
Ph
DMF, 40 C
N
CO Me
H
EtO C
2
2
CO Me
3
h
Ac
2
E-1a
1
a (E/Z = 1.1/1)
2a
0.15 mmol
3a
E-isomer only
0
.3 mmol
76% NMR yield
7
0% NMR yield
based on 1a
The control experiment indicated Z-isomer is more reactive than the E-isomer.
Typical procedure for the synthesis of 2-pyrroline 3a (Table 1, entry 3):
1
. 2,2-Diethyl 4-methyl 1-acetyl-5-benzyl-3-phenyl-1H-pyrrole-2,2,4(3H)-tricar-
boxylate.
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
3a
Under Ar, DBU (15.2 mg, 0.1 mmol) was added to a mixture of enyne 1a (E/Z = 1.1/1,
31.0 mg, 0.5 mmol) and 2-acetamidomalonate 2a (163.0 mg, 0.75 mmol) in dry
1
DMF (2.5 mL) at 40 ℃. The reaction was stirred at this temperature till the complete
consumption of 2a which was determined by TLC analysis. After cooling down to
room temperature, H O (5 mL) was added to the reaction mixture which was then
2
extracted by diethyl ether (3 × 10 mL). The combined organic phase was washed by
4
water and saturated aqueous NaCl solution and dried over MgSO . After filtration and
concentration, the residue was purified by column chromatography on silica gel (PE :
o
1
EA = 5 : 1) to give 3a in 90% (215.1 mg) yield as a white solid. m.p.: 87 ~ 88 C. H
NMR (300 MHz, CDCl
3
): δ = 7.35 ~ 7.15 (m, 10 H), 4.91 (d, J = 15.9 Hz, 1 H), 4.87
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(
s, 1 H), 4.70 (d, J = 15.9 Hz, 1 H), 4.38 ~ 4.16 (m, 2 H), 3.60 ~ 3.50 (m, 1 H), 3.45 (s,
H), 3.43 ~ 3.33 (m, 1 H), 2.06 (s, 3 H), 1.26 (t, J = 7.2 Hz, 3 H), 0.85 (m, J = 7.2 Hz,
3
3
1
5
1
4
1
3
H). C NMR (75.5 MHz, CDCl
3
): 169.55, 167.49, 164.75, 164.25, 153.73, 137.21,
36.63, 128.40 (2C), 127.78(2C), 127.62, 126.34, 112.41, 78.44, 62.52, 61.67, 54.11,
-1
1.07, 32.09, 24.62, 13.65, 13.11 ppm. IR (neat): v (cm ) 3444, 3029, 1759, 1687,
7
625, 1307, 1232, 1047, 1012, 699. HRMS calcd for C27H29NO : 479.1944, found:
+
79.1959. MS (70 eV): m/z (%): 479 (M , 0.60), 91 (100).
2
. 2,2-Diethyl 4-methyl 1-acetyl-5-(naphthalen-1-ylmethyl)-3-phenyl-1H-pyrrole
2,2,4(3H)-tricarboxylate.
-
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
3b
A mixture of 1b (E/Z = 1.5/1, 156.0 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol),
o
and DBU (15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 41 h to
1
afford 3b in the yield of 72% (190.4 mg). Colorless oil, H NMR (300 MHz,
CDCl
H), 7.64 ~ 7.51 (m, 3 H), 7.50 ~7.42 (m, 1 H), 7.36 ~ 7.26 (m, 5 H), 5.22 (d, J =
5.6 Hz, 1 H), 5.18 (d, J = 15.6 Hz, 1 H), 4.90 (s, 1 H), 4.47 ~ 4.27 (m, 2 H), 3.63
3.40 (m, 2 H), 3.44 (s, 3 H), 2.02 (s, 3 H), 1.38 (t, J = 7.2 Hz, 3 H), 0.93 (t, J =
3
): δ = 8.08 (d, J = 8.4 Hz, 1 H), 7.91 (d, J = 7.5 Hz, 1 H), 7.84 ~ 7.77 (m, 1
1
~
1
3
7
1
1
2
1
3
.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 169.49, 167.77, 164.98, 164.33,
53.05, 137.67, 133.77, 132.60, 131.44, 128.87, 127.99, 127.77, 127.50, 126.48,
25.88, 125.63, 124.11, 122.72, 113.16, 78.32, 62.67, 61.73, 53.87, 51.29, 30.02,
-1
4.11, 13.98, 13.39 ppm. IR (neat): v (cm ) 3488, 2993, 1749, 1706, 1664, 1630,
390, 1335 1226, 1059, 1018, 805, 698. HRMS calcd for C H NO : 529.2101,
3
1
31
7
+
found: 529.2094. MS (70 eV): m/z (%): 529 (M , 0.18), 141 (100).
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3
. 2,2-Diethyl 4-methyl 5-(4-methoxybenzyl)-1-acetyl-3-phenyl-1H-pyrrole-2,2,4
3H)-tricarboxylate
(
O
CH3
H CO
3
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
3c
A mixture of 1c (E/Z = 1.2/1, 146.0 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol),
o
and DBU (15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 29 h to
1
afford 3c in the yield of 70% (178.2 mg). Yellow oil, H NMR (300 MHz, CDCl
3
):
δ = 7.30 ~ 7.10 (m, 7 H), 6.86 (dd, J = 2.1, 6.6 Hz, 2 H), 4.84 (s, 1 H), 4.81 (d, J =
5.6 Hz, 1 H), 4.62 (d, J = 15.6 Hz, 1 H), 4.39 ~ 4.18 (m, 2 H), 3.78 (s, 3 H), 3.57
3.45 (m, 1 H), 3.48 (s, 3 H), 3.43 ~ 3.35 (m, 1 H), 2.09 (s, 3 H), 1.28 (t, J = 7.2
1
~
1
3
Hz, 3 H), 0.86 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl
64.94, 164.42, 158.20, 154.26, 137.36, 128.92, 128.67, 127.91, 127.73, 113.99,
12.36, 78.58, 62.67, 61.82, 55.12, 54.22, 51.22, 31.37, 24.74, 13.78, 13.25 ppm.
3
): 169.75, 167.67,
1
1
-1
IR (neat): v (cm ) 2984, 2953, 1746, 1707, 1620, 1511, 1369, 1223, 1133, 1019,
8
8
18, 700. HRMS calcd for C28H31NO : 509.2050, found: 509.2055. MS (70 eV):
+
m/z (%): 509 (M , 0.63), 121 (100).
4
. 2,2-Diethyl 4-methyl 5-(4-nitrobenzyl)-1-acetyl-3-phenyl-1H-pyrrole-2,2,4(3H)
tricarboxylate
-
A mixture of 1d (E/Z = 1.3/1, 153.6 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol),
o
and DBU (15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 1 h to
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o
1
afford 3d in the yield of 65% (170.3 mg). Yellow solid, m.p.: 134 ~ 135 C, H
NMR (300 MHz, CDCl ): δ = 8.16 (d, J = 8.7 Hz, 2 H), 7.47 (d, J = 8.7 Hz, 2 H),
.30 ~ 7.10 (m, 5 H), 4.99 (d, J = 15.6 Hz, 1 H), 4.94 (s, 1 H), 4.83 (d, J = 15.6 Hz,
H), 4.40 ~ 4.26 (m, 2 H), 3.58 ~ 3.50 (m, 1 H), 3.48 (s, 3 H), 3.47 ~ 3.37 (m, 1
3
7
1
1
3
H), 1.92 (s, 3 H), 1.31 (t, J = 7.2 Hz, 3 H), 0.86 (t, J = 7.2 Hz, 3 H). C NMR
75.5 MHz, CDCl ): 170.20, 167.89, 164.80, 164.64, 153.87, 146.65, 145.39,
36.82, 129.11, 128.16, 123.63, 112.67, 79.09, 63.28, 62.49, 55.38, 51.51, 32.90,
(
3
1
2
1
-
1
5.04, 13.92, 13.32 ppm. IR (neat): v (cm ) 2987, 2955, 1745, 1701, 1679, 1515,
346, 1306, 1233, 1048, 1003, 739, 698. HRMS calcd for C H N O : 524.1795,
2
7
28
2
9
+
found: 524.1796. MS (70 eV): m/z (%): 524 (M , 0.79), 409 (100).
5
. 2,2-Diethyl 4-methyl 1-acetyl-5-benzyl-3-(4-methoxyphenyl)-1H-pyrrole-2,2,4
3H)-tricarboxylate.
(
A mixture of 1e (E/Z = 1.3/1, 146.0 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol),
o
and DBU (15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 23 h to
o
1
afford 3e in the yield of 64% (162.9 mg); White solid, m.p.:105 ~ 106 C. H
NMR (300 MHz, CDCl ): δ = 7.36 ~ 7.13 (m, 7 H), 6.81 (dd, J = 1.5, 7.5 Hz, 2 H),
.87 (d, J = 15.9 Hz, 1 H), 4.82 (s, 1 H), 4.69 (d, J = 15.9 Hz, 1 H), 4.36 ~ 4.19 (m,
H), 3.77 (s, 3 H), 3.64 ~ 3.55 (m, 1 H), 3.58 ~ 3.43 (m, 4 H), 2.06 (s, 3 H), 1.27
3
4
2
1
3
(
t, J = 7.2 Hz, 3 H), 0.92 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl
3
):
69.86, 167.78, 165.07, 164.56, 159.18, 153.67, 136.91, 129.32, 128.59, 128.00,
26.52, 113.36, 112.92, 78.65, 62.70, 61.93, 55.17, 53.86, 51.34, 32.34, 24.86,
1
1
1
1
-1
3.85, 13.41 ppm. IR (neat): v (cm ) 2957, 2846, 2043, 1758, 1686, 1514, 1368,
8
284, 1232, 1052, 1013, 854, 731, 697. HRMS calcd for C28H31NO : 509.2050,
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+
found: 509.2069. MS (70 eV): m/z (%): 509 (M , 1.29), 91 (100).
6
. 2,2-Diethyl 4-methyl 1-acetyl-5-benzyl-3-(4-fluorophenyl)-1H-pyrrole-2,2,4
(
3H)-tricarboxylate.
A mixture of 1f (E/Z = 1.2/1, 140.0 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol), and
o
DBU (15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 4.5 h to afford
o
1
3
f in the yield of 89% (221.0 mg). White solid; m.p.:101 ~ 102 C. H NMR (300
MHz, CDCl ): δ = 7.36 ~ 7.20 (m, 7 H), 6.98 (t, J = 8.4 Hz, 2 H), 4.89 (d, J = 15.9 Hz,
H), 4.84 (s, 1 H), 4.65 (d, J = 15.9 Hz, 1 H), 4.37 ~ 4.19 (m, 2 H), 3.65 ~ 3.59 (m, 1
H), 3.58 ~ 3.44 (m, 4 H), 2.08 (s, 3 H), 1.27 (t, J = 7.2 Hz, 3 H), 0.92 (t, J = 7.2 Hz, 3
3
1
1
3
1
H). C NMR (75.5 MHz, CDCl ): 169.77, 167.59, 164.86, 164.41, 162.34 (d, J
F-C
=
3
4
2
46.9 Hz), 154.08, 136.69, 133.20 (d, JF-C = 3.0 Hz), 128.65, 127.93, 126.61, 114.91
2
(
d, JF-C = 21.1 Hz), 112.45, 78.47, 62.82, 62.02, 53.55, 51.37, 32.29, 24.85, 13.84,
-
1
1
1
4
3.40 ppm. IR (neat): v (cm ) 3067, 2983, 1756, 1706, 1672, 1622, 1506, 1380, 1227,
7
059, 1018, 1012, 861, 733, 698. HRMS calcd for C27H28NO F: 497.1850, found:
+
97.1856. MS (70 eV): m/z (%): 497 (M , 0.27), 91 (100).
7
. 2,2-Diethyl 3,4-dimethyl 1-acetyl-5-benzyl-1H-pyrrole-2,2,3,4(3H)-tetracarbo
xylate.
-
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
H CO
3
O
3g
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A mixture of 1g (E/Z = 3.2/1, 73.2 mg, 0.3 mmol), 2a (97.7 mg, 0.45 mmol), and
o
DBU (9.1 mg, 0.06 mmol) in 2.5 mL of DMF was stirred at 40 C for 3 h to
1
afford 3g in the yield of 81% (112.0 mg). Yellow oil, H NMR (300 MHz,
CDCl
3
): δ = 7.35 ~ 7.21 (m, 5 H), 4.68 (s, 2 H), 4.44 (s, 1 H), 4.34 ~ 4.25 (m, 2
H), 4.23 ~ 4.15 (m, 2 H), 3.73 (s, 3 H), 3.68 (s, 3 H), 2.16 (s, 3 H), 1.29 (t, J = 7.2
1
3
Hz, 3 H), 1.27 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl
3
): 169.58, 168.85,
66.93, 164.86, 164.41, 153.45, 135.74, 128.89, 127.62, 126.74, 110.04, 76.07,
3.08, 62.79, 53.07, 52.70, 51.64, 32.26, 24.46, 13.85, 13.72 ppm. IR (neat): v
1
6
-1
(
cm ) 2955, 2850, 1751, 1685, 1625, 1438, 1223, 1199, 1017, 733, 698. HRMS
+
calcd for C23
H
27NO
9
: 461.1686, found: 461.1689. MS (70 eV): m/z (%): 461 (M ,
1
.96), 91 (100).
8
. 2,2-Diethyl 4-methyl 1-acetyl-5-benzyl-3-methyl-1H-pyrrole-2,2,4(3H)-tricar-
boxylate.
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
CH3
3h
A mixture of 1h (E, 100.0 mg, 0.5 mmol), 2a (163.0 mg, 0.75 mmol), and DBU
o
(
15.2 mg, 0.10 mmol) in 2.5 mL of DMF was stirred at 40 C for 1.5 h to afford
1
3
7
3
h in the yield of 49% (102.2 mg). Yellow oil; H NMR (300 MHz, CDCl
3
): δ =
.31 ~ 7.24 (m, 2 H), 7.21 ~ 7.17 (m, 3 H), 4.59 (s, 2 H), 4.28 ~ 4.16 (m, 4 H),
1
3
.69 (s, 3 H), 3.62 (q, J = 6.9 Hz, 1 H), 2.09 (s, 3 H), 1.32 ~1.18 (m, 9 H). C
): 169.41, 167.70, 164.95, 164.93, 151.13, 136.39,
28.48, 127.53, 126.34, 115.23, 77.06, 62.24, 61.80, 51.13, 43.15, 31.94, 24.48,
NMR (75.5 MHz, CDCl
3
1
1
1
4
-1
6.68, 13.82, 13.69 ppm. IR (neat): v (cm ) 2983, 1745, 1707, 1679, 1619, 1371,
7
222, 1097, 1031, 729, 698. HRMS calcd for C22H27NO : 417.1788, found:
+
17.1806. MS (70 eV): m/z (%): 417 (M , 1.05), 91 (100).
9
. Diethyl 1,4-diacetyl-5-benzyl-3-phenyl-1H-pyrrole-2,2(3H)-dicarboxylate.
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O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
Me
3i
A solution of 1i (E, 123.0 mg, 0.5 mmol) in 1.5 mL of DMF was slowly added to a
solution of 2a (163.0 mg, 0.75 mmol) and DBU (15.2 mg, 0.10 mmol) in 1.0 mL
o
of DMF via syringe pump over 2 h at 40 C. After finishing addition, the mixture
was then stirred for another 26 h. After the routine work-up, 2-pyrroline 3i was
o
1
obtained in the yield of 70% (163.0 mg). White solid, m.p.:111 ~ 112 C. H NMR
300 MHz, CDCl ): δ = 7.36 ~ 7.12 (m, 10 H), 4.89 (s, 1 H), 4.87 (d, J = 15.6 Hz,
H), 4.64 (d, J = 15.6 Hz, 1 H), 4.39 ~ 4.29 (m, 1 H), 4.28 ~ 4.17 (m, 1 H), 3.62 ~
.50 (m, 1 H), 3.43 ~ 3.32 (m, 1 H), 2.07 (s, 3 H), 1.88 (s, 3 H), 1.25 (t, J = 7.2 Hz,
(
3
1
3
3
1
1
3
H), 0.85 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 195.48, 169.93,
3
67.51, 164.16, 152.82, 136.70, 136.63, 128.40, 128.26, 128.19, 127.84, 126.35,
119.96, 78.67, 62.63, 61.76, 54.88, 32.20, 29.92, 24.82, 13.63, 13.13 ppm. IR
-1
(
neat): v (cm ) 3463, 2986, 1759, 1740, 1669, 1574, 1378, 1222, 1063, 1026, 744,
7
6
00. HRMS calcd for C27H29NO : 463.1995, found: 463.2015. MS (70 eV): m/z
+
(
%): 463 (M , 3.80), 260 (100) ppm.
1
0. Diethyl 1,4-diacetyl-5-(4-methoxybenzyl)-3-phenyl-1H-pyrrole-2,2(3H)-dicar-
boxylate.
O
CH3
MeO
N
CO C H
2 5
2
O
CO C H
2 5
2
H C
3
3j
According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol), 1j (E, 82.8 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1 mg,
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o
0
.06 mmol) at 40 C for 70 h affords 3j in the yield of 61% (90.0 mg). Colorless
1
oil, H NMR (400 MHz, CDCl
3
): δ = 7.31 (bs, 4 H), 7.21 (d, J = 7.6 Hz, 3 H),
6
1
3
6
1
6
.87 (d, J = 8.0 Hz, 2 H), 4.89 (s, 1 H), 4.79 (d, J = 15.6 Hz, 1 H), 4.59 (d, J =
5.6 Hz, 1 H), 4.40 ~ 4.20 (m, 2 H), 3.79 (s, 3 H), 3.61 ~ 3.53 (m, 1 H) 3.46 ~
.37 (m, 1 H), 2.13 (s, 3 H), 1.90 (s, 3 H), 1.29 (t, J = 6.8 Hz, 3 H), 0.88 (t, J =
1
3
3
.8 Hz, 3 H). C NMR (100 MHz, CDCl ): 195.64, 170.08, 167.70, 164.32,
58.20, 153.36, 136.85, 128.98, 128.64, 128.40, 128.31, 119.90, 113.98, 78.79,
2.79, 61.90, 55.14, 54.96, 31.48, 30.09, 24.96, 13.77, 13.28 ppm. IR (neat): v
-1
(
cm ) 2983, 2836, 2253, 1747, 1672, 1579, 1512, 1343, 1222, 1053, 1030, 735,
7
701. HRMS calcd for C28H31NO : 493.2101, found: 493.2104. MS (70 eV): m/z
+
(
%): 493 (M , 11.87), 451 (100).
1
1. Diethyl 1,4-diacetyl-5-(4-nitrobenzyl)-3-phenyl-1H-pyrrole-2,2(3H)-dicarboxy
late.
-
O
CH3
O N
2
N
CO C H
2 5
2
O
CO C H
2 5
2
H C
3
3k
According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol), 1k (E, 87.3 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1 mg,
o
0
.06 mmol) at 40 C for 14 h affords 3k in the yield of 49% (75 mg). Yellow oil,
1
3
H NMR (400 MHz, CDCl ): δ = 8.19 (d, J = 8.8 Hz, 2 H), 7.48 (d, J = 8.8 Hz, 2
H), 7.35 (bs, 4 H), 7.15 (bs, 1 H), 5.00 (d, J = 15.6 Hz 1 H), 5.00 (s, 1 H), 4.81 (d,
J = 15.6 Hz, 1 H), 4.46 ~ 4.35 (m, 1 H), 4.35 ~ 4.27 (m, 1 H), 3.66 ~ 3.55 (m, 1
H), 3.50 ~ 3.41 (m, 1 H), 1.98 (s, 3 H), 1.89 (s, 3 H), 1.32 (t, J = 7.2 Hz, 3 H),
1
3
0
1
7
3
.90 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 195.78, 170.42, 167.75,
64.45, 152.89, 146.57, 145.40, 136.22, 129.14, 128.74, 128.64, 123.57, 119.78,
9.26, 63.34, 62.52, 55.96, 32.92, 30.13, 25.21, 13.87, 13.31 ppm. IR (neat): v
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-1
(
cm ) 2984, 2254, 1744, 1693, 1591, 1520, 1344, 1223, 1052, 1014, 860, 737,
28 2 8
701. HRMS calcd for C27H N O : 508.1846, found: 508.1845. MS (70 eV): m/z
+
(
%): 508 (M , 1.15), 43 (100).
1
2. Diethyl 1,4-diacetyl-5-benzyl-3-(4-methoxyphenyl)-1H-pyrrole-2,2(3H)-dicar-
boxylate.
According to the procedure of synthesis of 3i, the reaction of 2a (163.0 mg, 0.75
mmol), 1l (E, 136.0 mg, 0.5 mmol) in DMF under the catalysis of DBU (15.2 mg,
o
0
.10 mmol) at 40 C for 12 h affords 3l in the yield of 76% (187.4 mg). Yellow oil,
1
H NMR (300 MHz, CDCl
.823 (d, J = 15.9 Hz, 1 H), 4.824 (s, 1 H), 4.60 (d, J = 15.9 Hz, 1 H), 4.32 ~ 4.13
m, 2 H), 3.72 (s, 3 H), 3.64 ~ 3.48 (m, 2 H), 2.04 (s, 3 H), 1.85 (s, 3 H), 1.21 (t, J
3
): δ = 7.30 ~ 7.00 (m, 7 H), 6.80 (d, J = 8.1 Hz, 2 H),
4
(
1
3
=
7.2 Hz, 3 H), 0.88 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 195.59,
3
1
1
1
1
69.95, 167.54, 164.21, 159.42, 152.56, 136.73, 128.49, 128.35, 127.85, 126.29,
20.14, 113.61, 78.64, 62.54, 61.74, 55.00, 54.40, 32.16, 29.85, 24.83, 13.62,
-1
3.21 ppm. IR (neat): v (cm ) 2983, 2838, 1745, 1672, 1579, 1511, 1344, 1222,
029, 840, 736, 700. HRMS calcd for C H NO : 493.2101, found: 493.2121.
2
8
31
7
+
MS (70 eV): m/z (%): 493 (M , 5.24), 332 (100).
1
3. Diethyl 1,4-diacetyl-5-benzyl-3-(4-chlorophenyl)-1H-pyrrole-2,2(3H)-dicarbo-
xylate.
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According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol) and 1m (E, 84.0 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1
o
mg, 0.06 mmol) at 40 C for 17 h affords 3m in the yield of 69% (103.0 mg).
1
Yellow oil, H NMR (400 MHz, CDCl
3
): δ = 7.34 ~ 7.21 (m, 8 H), 7.14 (bs, 1 H),
4
.90 (s, 1 H), 4.87 (d, J = 15.6 Hz 1 H), 4.64 (d, J = 15.6 Hz, 1 H), 4.39 ~ 4.30 (m,
H), 4.28 ~ 4.19 (m, 1 H), 3.70 ~ 3.61 (m, 1 H), 3.57 ~ 3.47 (m, 1 H), 2.11 (s, 3
1
13
H), 1.92 (s, 3 H), 1.27 (t, J = 7.2 Hz, 3 H), 0.93 (t, J = 7.2 Hz, 3 H). C NMR
100 MHz, CDCl ): 195.17, 169.98, 167.42, 164.13, 153.19, 136.48, 135.41,
34.26, 128.55, 127.87, 126.56, 119.78, 78.56, 62.87, 62.04, 54.19, 32.30, 30.04,
(
3
1
2
1
-
1
4.93, 13.72, 13.29 ppm. IR (neat): v (cm ) 2983, 2253, 1747, 1673, 1583, 1492,
345, 1222, 1054, 1014, 735, 700. HRMS calcd for C H ClNO : 497.1605,
27
28
6
+
found: 497.1602. MS (70 eV): m/z (%): 497 (M , 2.46), 43 (100).
1
4. Diethyl 1-acetyl-4-benzoyl-5-benzyl-3-phenyl-1H-pyrrole-2,2(3H)-dicarboxyl-
ate.
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
3n
According to the procedure of synthesis of 3i, the reaction of 2a (163.0 mg, 0.75
mmol) and 1n (E, 154.0 mg, 0,5 mmol) in DMF under the catalysis of DBU (15.2
o
mg, 0.10 mmol) at 40 C for 20 h affords 3n in the yield of 66% (173.2 mg).
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1
Yellow oil, H NMR (300 MHz, CDCl
3
): δ = 7.63 ~ 7.58 (m, 2 H), 7.45 ~ 7.35 (m,
1
H), 7.31 ~ 7.24 (m, 4 H), 7.22 ~ 7.16 (m, 8 H), 5.19 (s, 1 H), 4.40 ~ 4.21 (m, 4
H), 3.53 (q, J = 7.2 Hz, 2 H), 2.03 (s, 3 H), 1.28 (t, J = 7.2 Hz, 3 H), 0.87 (t, J =
1
3
7
1
1
3
.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 192.78, 170.08, 167.59, 164.70,
50.50, 139.13, 136.75, 136.17, 132.10, 129.21, 128.39, 128.24, 128.03, 127.93,
26.50, 122.53, 78.41, 62.58, 61.96, 55.92, 33.49, 24.65, 13.75, 13.21 ppm. IR
-1
(
neat): v (cm ) 2983, 1743, 1674, 1600, 1451, 1369, 1236, 1056, 1004, 735, 697.
6
HRMS calcd for C32H31NO : 525.2151, found: 525.2145. MS (70 eV): m/z (%):
+
5
25 (M , 2.00), 105 (100).
1
5. Diethyl 1-acetyl-4-benzoyl-5-(4-methoxybenzyl)-3-phenyl-1H-pyrrole-2,2(3H)
dicarboxylate.
-
O
CH3
MeO
N
CO C H
2 5
2
O
CO C H
2 5
2
3o
According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol) and 1o (E, 101.4 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1
o
mg, 0.06 mmol) at 40 C for 16 h affords 3o in the yield of 65% (108.3 mg).
1
Yellow oil, H NMR (400 MHz, CDCl
3
): δ = 7.62 (d, J = 7.6 Hz, 2 H), 7.43 (t, J
=
7.2 Hz, 1 H), 7.31 (t, J = 7.2 Hz, 2 H), 7.22 ~ 7.16 (m, 5 H), 7.13 (d, J = 8.0 Hz,
H), 6.83 (d, J = 8.0 Hz, 2 H), 5.10 (s, 1 H), 4.40 ~ 4.26 (m, 2 H), 4.25 (d, J =
6.4 Hz, 1 H), 4.15 (d, J = 16.4 Hz, 1 H), 3.77 (s, 3 H), 3.54 (q, J = 6.8 Hz, 2 H),
2
1
2
1
3
.08 (s, 3 H), 1.31 (t, J = 6.8 Hz, 3 H), 0.88 (t, J = 6.8 Hz, 3 H). C NMR (100
): 192.88, 170.13, 167.69, 164.81, 158.22, 150.86, 139.21, 136.27,
32.16, 129.26, 129.00, 128.72, 128.30, 128.12, 128.01, 127.96, 122.41, 113.89,
8.45, 62.64, 62.02, 55.91, 55.13, 32.71, 24.71, 13.83, 13.29 ppm. IR (neat): v
MHz, CDCl
3
1
7
-1
(
cm ) 2981, 2253, 1744, 1610, 1512, 1369, 1242, 1177, 1056, 1030, 725, 698.
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7
HRMS calcd for C33H33NO : 555.2257, found: 555.2266. MS (70 eV): m/z (%):
+
5
55 (M , 4.31), 43 (100).
1
6. Diethyl 1-acetyl-4-benzoyl-5-benzyl-3-(4-methoxyphenyl)-1H-pyrrole-2,2(3H)
dicarboxylate.
-
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
OMe
3p
According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol) and 1p (E, 101.4 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1
o
mg, 0.06 mmol) at 40 C for 28 h affords 3p in the yield of 67% (112.0 mg).
1
Yellow oil, H NMR (400 MHz, CDCl
3
): δ = 7.63 (d, J = 7.2 Hz, 2 H), 7.43 (t, J
=
7.2 Hz, 1 H), 7.34 ~ 7.25 (m, 4 H), 7.22 ~ 7.18 (m, 3 H), 7.14 (d, J = 8.0 Hz, 2
H), 6.74 (d, J = 8.0 Hz, 2 H), 5.14 (s, 1 H), 4.38 ~ 4.21 (m, 4 H), 3.70 (s, 3 H),
.61 (q, J = 6.8 Hz, 2 H), 2.04 (s, 3 H), 1.29 (t, J = 7.2 Hz, 3 H), 0.94 (t, J = 7.2
3
1
3
Hz, 3 H). C NMR (100 MHz, CDCl ): 192.91, 170.13, 167.66, 164.78, 159.21,
3
1
1
1
50.16, 139.12, 136.83, 132.15, 130.37, 128.41, 128.27, 128.08, 128.04, 127.95,
26.51, 122.78, 113.35, 78.38, 62.57, 62.00, 55.43, 55.02, 33.50, 24.70, 13.79,
-1
3.35 ppm. IR (neat): v (cm ) 2982, 2837, 2253, 1744, 1608, 1511, 1447, 1243,
1
5
177, 1056, 1030, 732, 698. HRMS calcd for C H NO : 555.2257, found:
3
3
33
7
+
55.2261. MS (70 eV): m/z (%): 555 (M , 3.90), 105 (100).
1
7. Diethyl 1-acetyl-5-benzyl-4-(4-methoxybenzoyl)-3-phenyl-1H-pyrrole-2,2(3H)
dicarboxylate.
-
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O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
MeO
3q
According to the procedure of synthesis of 3i, the reaction of 2a (97.7 mg, 0.45
mmol) and 1q (E, 101.4 mg, 0.3 mmol) in DMF under the catalysis of DBU (9.1
o
mg, 0.06 mmol) at 40 C for 46 h affords 3q in the yield of 61% (101.6 mg).
1
Yellow oil, H NMR (400 MHz, CDCl
3
): δ = 7.74 (d, J = 8.0 Hz, 2 H), 7.34 ~
7
.14 (m, 10 H), 6.83 (d, J = 8.4 Hz, 2 H), 5.24 (s, 1 H), 4.40 ~ 4.17 (m, 4 H), 3.80
(s, 3 H), 3.54 (q, J = 6.8 Hz, 2 H), 2.03 (s, 3 H), 1.29 (t, J = 6.8 Hz, 3 H), 0.88 (t,
1
3
J = 6.8 Hz, 3 H). C NMR (100 MHz, CDCl
3
): 191.19, 170.04, 167.72, 164.91,
63.18, 148.72, 136.90, 136.15, 131.50, 130.93, 129.31, 128.41, 128.03, 127.99,
26.53, 122.94, 113.63, 78.40, 62.61, 62.02, 56.25, 55.32, 33.79, 24.63, 13.81,
1
1
1
-1
3.28 ppm. IR (neat): v (cm ) 2981, 2253, 1744, 1676, 1598, 1455, 1304, 1247,
1
5
169, 1055, 1026, 847, 734, 699. HRMS calcd for C33 : 555.2257, found:
H33NO
7
+
55.2260. MS (70 eV): m/z (%): 555 (M , 2.83), 135 (100).
1
8. Diethyl 1-acetyl-5-benzyl-4-(4-chlorobenzoyl)-3-phenyl-1H-pyrrole-2,2(3H)-
dicarboxylate.
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
Cl
3r
According to the procedure of synthesis of 3i, the reaction of 2a (163.0 mg, 0.75
mmol) and 1r (E, 171.5 mg, 0.5 mmol) in DMF under the catalysis of DBU (15.2
o
mg, 0.10 mmol) at 40 C for 16 h affords 3r in the yield of 74% (206.8 mg).
1
Orange oil, H NMR (300 MHz, CDCl
3
): δ = 7.56 (d, J = 8.4 Hz, 2 H), 7.32 ~
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This journal is © The Royal Society of Chemistry 2012
7.18 (m, 12 H), 5.16 (s, 1 H), 4.38 ~ 4.20 (m, 4 H), 3.54 (q, J = 7.2 Hz, 2 H), 2.04
1
3
(
s, 3 H), 1.29 (t, J = 7.2 Hz, 3 H), 0.87 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz,
CDCl ): 191.48, 170.10, 167.56, 164.63, 151.04, 138.37, 137.47, 136.60, 136.01,
29.45, 129.17, 128.56, 128.46, 128.02, 127.91, 126.60, 122.08, 78.46, 62.67,
3
1
6
1
-1
2.04, 55.89, 33.55, 24.69, 13.76, 13.22 ppm. IR (neat): v (cm ) 3267, 2995, 1755,
720, 1641, 1611, 1386, 1258, 1219, 1061, 1014, 766, 702. HRMS calcd for
+
C
32
H30NO
6
Cl: 559.1762, found: 559.1757. MS (70 eV): m/z (%): 559 (M , 1.42),
139 (100).
1
9. Diethyl 1-acetyl-5-benzyl-4-(methylsulfonyl)-3-phenyl-1H-pyrrole-2,2(3H)-di-
carboxylate.
O
CH3
N
CO C H
2 5
2
O
S
CO C H
2 2 5
O
3s
The reaction of 2a (163.0 mg, 0.75 mmol) and 1s (E, 172 mg, 0.5 mmol) in DMF
o
under the catalysis of DBU (15.2 mg, 0.10 mmol) at 40 C for 22 h affords 3s in
o
1
the yield of 51% (143.0 mg). White solid, m.p.: 90 ~91 C. H NMR (300 MHz,
CDCl ): δ = 7.35 ~ 7.01 (m, 13 H), 6.86 (t, J = 7.5 Hz, 1 H), 6.72 (d, J = 7.5 Hz,
3
1
4
H), 4.94 (s, 1 H), 4.85 (d, J = 15.6 Hz, 1 H), 4.52 (d, J = 15.6 Hz, 1 H), 4.21 ~
.03 (m, 2 H), 3.44 ~ 3.37 (m, 2 H), 1.84 (s, 3 H), 1.11 (t, J = 7.2 Hz, 3 H), 0.74 (t,
1
3
J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ): 170.59, 166.70, 164.04, 153.44,
3
1
41.65, 135.76, 134.24, 132.72, 130.31, 128.81, 128.54, 128.15, 127.94, 127.83,
27.21, 126.73, 121.66, 79.19, 63.00, 62.39, 55.84, 31.81, 25.17, 13.67, 13.19
1
-1
ppm. IR (neat): v (cm ) 3503, 2926, 1760, 1740, 1695, 1613, 1305, 1265, 1229,
150, 1106, 1080, 1018, 725, 699. HRMS calcd for C H NO S: 561.1821,
1
3
1
31
7
+
found: 561.1818. MS (70 eV): m/z (%): 561 (M , 0.26), 233 (100).
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2
0. Diethyl 1-acetyl-5-benzyl-4-cyano-3-phenyl-1H-pyrrole-2,2(3H)-dicarboxylat-
e.
The reaction of 2a (163.0 mg, 0.75 mmol) and 1t (E, 114.5 mg, 0.5 mmol) in
o
DMF under the catalysis of DBU (15.2 mg, 0.10 mmol) at 40 C for 0.5 h affords
o
1
3
t in the yield of 80% (178.0 mg). Orange solid, m.p.:119 ~ 120 C. H NMR
300 MHz, CDCl ): δ = 7.39 ~ 7.26 (m, 10 H), 4.81 (s, 1 H), 4.48 (d, J = 15.9 Hz,
H), 4.35 (d, J = 15.9 Hz, 1 H), 4.38 ~ 4.28 (m, 2 H), 3.60 ~ 3.40 (m, 2 H), 2.03
(
3
1
1
3
(
s, 3 H), 1.31 (t, J = 6.9 Hz, 3 H), 0.87 (t, J = 6.9 Hz, 3 H). C NMR (75.5 MHz,
CDCl ): 168.95, 167.04, 163.75, 157.28, 135.04, 134.14, 129.26, 128.88, 128.43,
27.83, 127.24, 115.48, 94.51, 79.22, 63.11, 62.30, 54.28, 54.23, 34.47, 24.32,
3
1
1
1
-1
3.87, 13.25 ppm. IR (neat): v (cm ) 3461, 2928, 2210, 1757, 1741, 1678, 1625,
379, 1362, 1236, 1058, 1008, 737, 697. HRMS calcd for C26 : 446.1842,
CO ]), 21.40), 43
26 2 5
H N O
+
+
+
found: 446.1863. MS (70 eV): m/z (%): 404 (M +H -[CH
3
(
100).
2
1. Diethyl 1-acetyl-5-benzyl-4-formyl-3-phenyl-1H-pyrrole-2,2(3H)-dicarboxyl
ate.
-
O
CH3
N
CO C H
2 5
2
O
CO C H
2 5
2
H
3u
According to the procedure of synthesis of 3i, the reaction of 2a (163.0 mg, 0.75
mmol) and 1u (E, 116.0 mg, 0.5 mmol) in DMF under the catalysis of DBU (15.2
SI-17

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o
mg, 0.10 mmol) at 40 C for 10 h affords 3u in the yield of 55% (123.0 mg).
1
Yellow oil, H NMR (300 MHz, CDCl
3
): δ = 9.89 (s, 1 H), 7.39 ~ 7.26 (m, 10 H),
.92 (s, 1 H), 4.66 (d, J = 16.2 Hz, 1 H), 4.61 (d, J = 16.2 Hz, 1 H), 4.37 ~ 4.20 (m,
H), 3.60 ~ 3.39 (m, 2 H), 2.05 (s, 3 H), 1.30 (t, J = 7.2 Hz, 3 H), 0.88 (t, J = 7.2
4
2
1
3
Hz, 3 H). C NMR (75.5 MHz, CDCl
3
): 185.05, 170.01, 167.29, 164.26, 157.87,
1
5
1
36.01, 135.71, 128.75, 127.94, 127.88, 127.03, 122.24, 79.22, 62.87, 62.10,
-1
3.29, 31.44, 24.86, 13.74, 13.18 ppm. IR (neat): v (cm ) 2919, 2850, 1743, 1684,
652, 1613, 1454, 1261, 1208, 1055, 1015, 803, 739, 698. HRMS calcd for
+
C
26
H27NO
6
: 449.1838, found: 449.1845. MS (70 eV): m/z (%): 449 (M , 5.06), 91
(100).
2
2. Trimethyl 1-acetyl-5-benzyl-3-phenyl-1H-pyrrole-2,2,4(3H)-tricarboxylate.
The reaction of 1a (E/Z = 1.1/1, 131.0 mg, 0.5 mmol) and 2b (141.8 mg, 0.75
o
mmol) in DMF under the catalysis of DBU (15.2 mg, 0.10 mmol) at 40 C for 10
o
1
h affords 3v in the yield of 93% (210.0 mg). White solid, m.p.: 119-120 C. H
NMR (400 MHz, CDCl ): δ = 7.35 ~ 7.20 (m, 10 H), 4.94 (d, J = 16.0 Hz, 1 H),
.82 (s, 1 H), 4.67 (d, J = 16.0 Hz, 1 H), 3.83 (s, 3 H), 3.48 (s, 3 H), 3.05 (s, 3 H),
3
4
2
1
5
1
1
3
.11 (s, 3 H). C NMR (100 MHz, CDCl ): 169.54, 168.11, 164.78, 164.65,
3
53.38, 137.26, 136.41, 128.60, 127.93, 127.80, 127.76, 126.53, 112.70, 78.62,
-1
4.17, 53.38, 52.09, 51.23, 32.18, 24.54 ppm. IR (neat): v (cm ) 2950, 2889,
741, 1703, 1672, 1631, 1438, 1391, 1242, 1207, 1067, 986, 740, 721, 671.
HRMS calcd for C25
H25NO
7
: 451.1631, found: 451.1635. MS (70 eV): m/z (%):
+
4
51 (M , 0.80), 43 (100).
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2
3. 1-tert-Butyl 2,2-diethyl 4-methyl 5-benzyl-3-phenyl-1H-pyrrole-1,2,2,4(3H)-te
tracarboxylate.
-
Boc
N
CO C H
2 5
2
O
CO C H
2 5
2
H CO
3
3w
The reaction of 1a (E/Z = 1.1/1, 131.0 mg, 0.5 mmol) and 2c (156.0 mg, 0.75
o
mmol) in DMF under the catalysis of DBU (15.2 mg, 0.10 mmol) at 40 C for 3.5
o
1
h affords 3w in the yield of 80% (215.0 mg). White solid, m.p.: 87~88 C. H
NMR (300 MHz, CDCl ): δ = 7.39 (d, J = 7.2 Hz, 2 H), 7.34 ~ 7.18 (m, 8 H),
.93 (d, J = 14.7 Hz, 1 H), 4.79 (s, 1 H), 4.78 (d, J = 14.7 Hz, 1 H), 4.38 ~ 4.23
m, 2 H), 3.60 ~ 3.54 (m, 1 H) 3.48 (s, 3 H), 3.35 ~ 3.29 (m, 1 H), 1.28 (t, J = 7.2
3
4
(
1
3
Hz, 3 H), 1.26 (s, 9 H), 0.87 (t, J = 7.2 Hz, 3 H). C NMR (75.5 MHz, CDCl ):
3
1
1
1
68.18, 165.11, 164.71, 155.66, 150.40, 138.10, 137.88, 128.29, 128.07, 127.85,
27.55, 125.99, 109.02, 83.11, 77.89, 62.37, 61.49, 54.66, 51.04, 31.98, 27.55,
-1
3.98, 13.35 ppm. IR (neat): v (cm ) 2979, 1754, 1727, 1702, 1625, 1368, 1226,
1
153, 1009, 731, 705. HRMS calcd for C30 : 537.2363, found: 537.2358.
H35NO
8
+
MS (70 eV): m/z (%): 537 (M , 1.82), 57 (100).
2
4. 1-Benzyl 2,2-diethyl 4-methyl 5-benzyl-3-phenyl-1H-pyrrole-1,2,2,4(3H)-tetra
carboxylate.
-
Cbz
N
CO C H
2
2
5
O
CO C H
2 5
2
H CO
3
3x
The reaction of 1a (E/Z = 1.1/1, 78.6 mg, 0.3 mmol) and 2d (139.0 mg, 0.45
o
mmol) in DMF under the catalysis of DBU (9.1 mg, 0.06 mmol) at 40 C for 11 h
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1
affords 3x in the yield of 93% (159.0 mg). Colorless oil, H NMR (400 MHz,
CDCl ): δ = 7.34 ~ 7.18 (m, 13 H), 7.11 ~ 7.08 (m, 2 H), 5.00 (s, 2 H), 4.90 (d, J
14.4 Hz, 1 H), 4.85 (s, 1 H), 4.78 (d, J = 14.4 Hz, 1 H), 4.27 ~ 4.15 (m, 2 H),
.49 (s, 3 H), 3.34 ~ 3.25 (m, 1 H), 3.20 ~ 3.10 (m, 1 H), 1.17 (t, J = 7.2 Hz, 3 H),
3
=
3
0
1
1
3
.68 (t, J = 7.2 Hz, 3 H). C NMR (100 MHz, CDCl
55.11, 151.66, 137.67, 137.42, 134.81, 128.27, 128.22, 127.89, 127.67, 126.08,
10.14, 77.85, 77.20, 67.99, 62.57, 61.59, 54.95, 51.19, 32.10, 13.77, 13.16 ppm.
3
): 168.00, 164.92, 164.30,
1
-1
IR (neat): v (cm ) 2986, 2901, 1737, 1702, 1631, 1393, 1226, 1056, 1018, 740,
6
97. HRMS calcd for C H NO : 571.2206, found: 571.2205. MS (70 eV): m/z
3
3
33
8
+
(
%): 571 (M , 1.28), 91 (100).
2
5. 2,2-Diethyl 4-methyl 5-benzyl-3-phenyl-1H-pyrrole-2,2,4(3H)-tricarboxylate.
The reaction of 1a (E/Z = 1.1/1, 52.4 mg, 0.2 mmol), 2e (50.8 mg, 0.24 mmol)
o
and DBU (42.6 mg, 0.28 mmol) in DMF at 40 C for 2 h affords 3y in the yield of
o
1
8
7
7% (76.0 mg). White solid, m.p.: 97-98 C. H NMR (400 MHz, CDCl
.38 ~ 7.16 (m, 10 H), 5.05 (s, 1 H), 4.85 (s, 1 H), 4.43 (d, J = 15.2 Hz, 1 H), 4.17
4.04 (m, 2 H), 4.00 (d, J = 15.2 Hz, 1 H), 3.71 ~ 3.64 (m, 1 H), 3.56 ~ 3.48 (m,
3
): δ =
~
1
1
3
H), 3.51 (s, 3 H), 1.09 (t, J = 7.2 Hz, 3 H), 0.77 (t, J = 7.2 Hz, 3 H). C NMR
): 168.57, 167.14, 165.82, 159.23, 138.95, 136.38, 128.80,
28.75, 128.53, 127.83, 127.16, 126.97, 102.93, 76.92, 62.36, 61.80, 53.42, 50.44,
(100 MHz, CDCl
3
1
3
1
-
1
3.39, 13.72, 13.27. IR (neat): v (cm ) 3371, 2994, 2885, 2814, 1726, 1678, 1598,
432, 1267, 1211, 1130, 1094, 1052, 776, 739, 702 ppm. HRMS calcd for
+
C H NO : 437.1838, found: 437.1839. MS (70 eV): m/z (%): 437 (M , 44.80),
2
5
27
6
91 (100).
SI-20

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Synthesis of 3y from 2-pyrroline 3w: 2-Pyrroline 3w (126.7 mg, 0.29 mmol) was
o
dissolved in 4 mL of CH
and the mixture was stirred for 30 min, then was stirred for overnight. After the
reaction was complete, 4 mL of H O was added and the aqueous phase was
neutralized by 1 N NaOH. The reaction mixture was then extracted with CH Cl
3 x 5 mL) and the combined organic phase was washed successively with
2 2 3 2
Cl under 0 C, CF CO H (1 mL, 14.5 mmol) was added
2
2
2
(
3
saturated NaHCO , NaCl and dried over anhydrous MgSO4. After removal of
solvent under vacuum, the residue was purified by column chromatography on
silica gel to give 84% (106 mg) of 3y.
The procedure for the synthesis of pyrrole 4
2
6. dimethyl 1-acetyl-5-benzyl-3-phenyl-2,3-dihydro-1H-pyrrole-2,4-dicarboxylat
–
e.
O
CH3
N
O
CO CH
2
3
H CO
3
4
A mixture of 3v (270.6 mg, 0.6 mmol), lithium chloride (32.5 mg, 0.75 mmol),
and water (15.5 mg, 0.85 mmol) in 2.0 mL of anhydrous dimethylformamide
o
under nitrogen was stirred at 160-165 C,. The solution immediately became
cloudy and began evolving CO . After stirring for 1h, the reaction mixture was
2
cooling down and poured into 15 mL water with vigorous stirring. The gummy
solid which formed was collected by filtration through glass wool, dissolved in
dichloromethane, and dried with anhydrous MgSO4. After the solution was
concentrated under vacuum, the residual product was purified by column
chromatography on silica gel to give white solid; yield: 54% (127.0 mg). m.p.:
o
1
1
3
34~135 C. H NMR (400 MHz, CDCl ): δ = 7.36 ~ 7.20 (m, 10 H), 4.92 (d, J =
1
4.8 Hz, 1 H), 4.30 (d, J = 14.8 Hz, 1 H), 4.59 (bs, 1 H), 4.29 (s, 1 H), 3.76 (s, 3
SI-21

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This journal is © The Royal Society of Chemistry 2012
1
3
H) 3.58 (s, 3 H), 2.00 (s, 3 H). C NMR (100 MHz, CDCl
3
): 170.63, 168.85,
1
5
1
65.24, 141.78, 137.15, 128.95, 128.51, 128.29, 127.59, 126.62, 126.32, 69.31,
-1
2.87, 51.30, 49.90, 32.65, 24.29 ppm. IR (neat): v (cm ) 2954, 2924, 2853, 1743,
704, 1672, 1631, 1439, 1391, 1243, 1207, 1089, 986, 747, 721, 693. HRMS
+
calcd for C23
H
23NO
5
: 393.1576, found: 393.1578. MS (70 eV): m/z (%): 393 (M ,
1
4.52), 91 (100).
X-ray crystal structure of 3e.
SI-22

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
1
80
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10 ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
1
0
9
8
7
6
5
4
3
2
1
ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
2
00 190 180 170 160 150 140 130 120 110 100
90
80
70
60
50
40
30
20
10 ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
2
00
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10 ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
9
.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5 ppm

Electronic Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2012
1
90
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10 ppm