N-heterocyclic carbene-promoted [3+2] cycloaddition of allenyl sulfone and arylidenemalononitriles

Article abstract of DOI:10.3987/COM-16-S(S)8

N-Heterocyclic carbenes promote the [3+2] cycloaddition of allenyl sulfone and arylidenemalononitriles, accompanied by 1,2-migration of the sulfonyl group. This reaction provides a new route to highly substituted cyclopentenes.

Full text of DOI:10.3987/COM-16-S(S)8

N-Heterocyclic Carbene-Promoted [3+2] Cycloaddition
of Allenyl Sulfone and Arylidenemalononitriles
Satoru Kuwano,* Toshinobu Masuda, Koki Yamaguchi, and Takayoshi Arai
Supporting information
Contents
1. General................................................................................................................................................................ S2
2. Preparation of arylidenemalononitriles......................................................................................................... S2
3. NHC-promoted [3+2] cyclization of allenyl sulfone and arylidenemalononitrile............................... S5
4. NMR spectra ...................................................................................................................................................... S9
5. Single Crystal X-Ray Analysis of 4d.......................................................................................................... S23
S1

1. General
Dry solvents were purchased from commercial suppliers and used without further purification. Analytical thin-layer
chromatography (TLC) was performed on glass plates coated with 0.25 mm 230-400 mesh silica gel containing a
fluorescent indicator (Merck, #1.05715.0009). Silica gel column chromatography was performed on Kanto silica gel
1
60 (spherical, 100-210 m). IR spectra were recorded on JASCO FT/IR-4100 using ATR. H-NMR spectra were
recorded on JEOL ECS-400 (400MHz) spectrometers. Chemical shifts of 1H-NMR spectra were reported relative to
tetramethyl silane (0) or acetone–d6 (δ 2.05). 13C-NMR spectra were recorded on JEOL ECS-400 (100MHz)
spectrometers. Chemical shifts of 13C-NMR spectra were reported relative to CDCl3 ( 77.0) or acetone–d6 (δ 29.84).
Splitting patterns were reported as s, singlet; d, doublet; t, triplet; m, multiplet.
2. Preparation of arylidenemalononitriles
Arylidenemalononitriles 3b–n were prepared through Knoevenagel condensation of the corresponding aldehydes
with malononitrile and recrystallized from EtOH and hexane, according to the literature.1
2-(4-Fluorobenzylidene)malononitrile (3b)
Pale pink solids; Rf=0.50 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.98-7.95 (m,
2H), 7.74 (s, 1H), 7.26-7.21 (m, 2H); 13C NMR (100MHz, CDCl3) δ 160.1 (d, 1JCF = 264.1
3
2
Hz), 158.3, 133.4 (d, JCF = 9.5 Hz), 127.3, 117.1 (d, JCF = 21.9 Hz), 113.5, 112.5, 82.3;
HRMS calcd for C10H4FN2 [M－H]+: 171.0359, found: m/z 171.0358; IR (neat) 2231, 1595, 1575, 1506, 1416, 1382,
1306, 1242, 1163 cm-1.
2-(4-Chlorobenzylidene)malononitrile (3c)
White solids; Rf=0.53 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.86 (d, J = 8.5
Hz, 1H), 7.73 (s, 1H), 7.52 (d, J = 8.5 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 158.3, 141.1,
131.8, 130.1, 129.2, 113.4, 112.3, 83.3; HRMS calcd for C10H4ClN2 [M－H]+: 187.0063,
found: m/z 187.0065; IR (neat) 2227, 1587, 1276, 1103, 1088 cm-1.
2-(4-Bromobenzylidene)malononitrile (3d)
White solids; Rf=0.53 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.78 (d, J = 8.9
Hz, 1H), 7.72 (s, 1H), 7.69 (d, J = 8.9 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 158.4, 133.0,
131.8, 129.9, 129.6, 113.4, 112.3, 83.4; HRMS calcd for C10H4BrN2 [M－H]+: 230.9558,
found: m/z 230.9565; IR (neat) 2229, 1578, 1276, 1259 cm-1.
2-(4-Iodobenzylidene)malononitrile (3e)
White solids; Rf=0.53 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.91 (d, J = 8.5
Hz, 1H), 7.70 (s, 1H), 7.60 (d, J = 8.5 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 158.7, 139.0,
131.4, 130.0, 113.4, 112.3, 102.8, 83.4; HRMS calcd for C10H4IN2 [M－H]+: 278.9419,
found: m/z 278.9430; IR (neat) 2225, 1576, 1397, 1275 cm-1.
1
J. S. Yadav, B.V.S. Reddy, A.K. Basak, B. Visali, A.V. Narsaiah, K. Nagaiah, Eur. J. Org. Chem. 2004, 546.
S2

2-(4-Nitrobenzylidene)malononitrile (3f)
1
Pale brown solids; Rf=0.47 (hexane:EtOAc = 3:1); H NMR (400MHz, CDCl3) δ 8.41-
8.38 (m, 2H), 8.10-8.06 (m, 2H), 7.88 (s, 1H); 13C NMR (100MHz, CDCl3) δ 156.9, 150.3,
135.8, 131.3, 124.6, 112.6, 111.6, 87.4; HRMS calcd for C10H4N3O2 [M－H]+: 198.0304,
found: m/z 198.0305; IR (neat) 2230, 1579, 1521, 1343, 1213 cm-1.
2-(4-Methylbenzylidene)malononitrile (3g)
Gray solids; Rf=0.53 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.82 (d, J = 8.2
Hz, 1H), 7.72 (s, 1H), 7.84 (d, J = 8.2 Hz, 1H), 2.46 (s, 3H); 13C NMR (100MHz, CDCl3)
δ 159.8, 146.4, 130.9, 130.3, 128.4, 114.0, 112.8, 81.1, 22.0; HRMS calcd for C11H7N2 [M
－H]+: 167.0609, found: m/z 167.0609; IR (neat) 2224, 1605, 1587, 1509, 1412, 1375, 1302, 1221, 1191 cm-1.
2-(3-Fluorobenzylidene)malononitrile (3h)
1
White solids; Rf=0.50 (hexane:EtOAc = 3:1); H NMR (400MHz, CDCl3) δ 7.76 (s, 1H),
7.69-7.62 (m, 2H), 7.57-7.52 (m, 1H), 7.37-7.30 (m, 1H); 13C NMR (100MHz, CDCl3) δ
162.7 (d, 1JCF = 253.7 Hz), 158.3, 132.5 (d, 3JCF = 8.6 Hz), 131.4 (d, 3JCF = 7.6 Hz), 126.7,
2
2
121.6 (d, JCF = 21.0 Hz), 116.8 (d, JCF = 22.8 Hz), 113.2, 112.0, 84.6; HRMS calcd for C10H4FN2 [M－H]+:
171.0359, found: m/z 171.0358; IR (neat) 2229, 1597, 1576, 1492, 1432, 1301, 1276, 1263, 1156 cm-1.
2-(3-Chlorobenzylidene)malononitrile (3i)
White solids; Rf=0.53 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.85-7.83 (m,
2H), 7.73 (s, 1H), 7.62-7.59 (m, 1H), 7.52-7.48 (m, 1H); 13C NMR (100MHz, CDCl3) δ
158.2, 135.8, 134.3, 132.3, 130.9, 130.4, 128.3, 113.2, 112.0, 84.6; HRMS calcd for
C10H4ClN2 [M－H]+: 187.0063, found: m/z 187.0066; IR (neat) 2230, 1591, 1559, 1478, 1417, 1366, 1293, 1266,
1215, 1098, 1080 cm-1.
2-(3-Bromobenzylidene)malononitrile (3j)
1
Pale gray solids; Rf=0.50 (hexane:EtOAc = 3:1); H NMR (400MHz, CDCl3) δ 7.93-7.89
(m, 2H), 7.77-7.75 (m, 1H), 7.71 (s, 1H), 7.46-7.42 (m, 1H); 13C NMR (100MHz, CDCl3)
δ 158.1, 137.2, 133.4, 132.5, 131.1, 128.6, 123.6, 113.1, 112.0, 84.6; HRMS calcd for
C10H4BrN2 [M－H]+: 230.9558, found: m/z 230.9564; IR (neat) 2229, 1557, 1476, 1415, 1293, 1267, 1212 cm-1.
2-(3-Iodobenzylidene)malononitrile (3k)
Pale yellow solids; Rf=0.56 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 8.14-8.13
(m, 1H), 7.97-7.94 (m, 2H), 7.68 (s, 1H), 7.31-7.27 (m, 1H); 13C NMR (100MHz, CDCl3) δ
158.0, 143.1, 139.4, 132.6, 131.0, 129.0, 113.2, 112.0, 94.8, 84.3; HRMS calcd for C10H4IN2
[M－H]+: 278.9419, found: m/z 278.9430; IR (neat) 2226, 1591, 1411, 1214 cm-1.
S3

2-(3-Methylbenzylidene)malononitrile (3l)
White solids; Rf=0.56 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.74-7.70 (m,
3H), 7.45-7.41 (m, 2H), 2.43 (s, 3H); 13C NMR (100MHz, CDCl3) δ 160.1, 139.6, 135.5,
131.2, 130.9, 129.5, 127.9, 113.8, 112.6, 82.4, 21.2; HRMS calcd for C11H7N2 [M－H]+:
167.0609, found: m/z 167.0609; IR (neat) 2226, 1574, 1303, 1267, 1251, 1180 cm-1.
2-(3-Methoxybenzylidene)malononitrile (3m)
Pale yellow solids; Rf=0.50 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 7.75 (s,
1H), 7.50-7.41 (m, 3H), 7.19-7.16 (m, 1H), 3.87 (s, 3H); 13C NMR (100MHz, CDCl3) δ
160.0, 159.9, 132.0, 130.5, 123.9, 121.3, 114.0, 113.6, 112.6, 82.8, 55.5; HRMS calcd for
C11H7N2O [M－H]+: 183.0558, found: m/z 183.0560; IR (neat) 2229, 1595, 1496, 1466, 1270, 1248, 1163 cm-1.
2-(Naphthalen-2-ylmethylene)malononitrile (3n)
Yellow solids; Rf=0.54 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 8.28 (s, 1H),
8.07 (dd, J = 1.6, 8.8 Hz, 1H), 7.98-7.91 (m, 3H), 7.89 (s, 1H), 7.71-7.59 (m, 2H); 13C
NMR (100MHz, CDCl3) δ 159.6, 135.7, 134.4, 132.4, 129.9, 129.56, 129.52, 128.4, 127.9,
127.6, 124.0, 113.9, 112.8, 82.0; HRMS calcd for C14H7N2 [M－H]+: 203.0609, found: m/z 203.0612; IR (neat) 2224,
1583, 1269, 1245 cm-1.
2-(2-Methylbenzylidene)malononitrile (3o)
White solids; Rf=0.64 (hexane:EtOAc = 3:1); 1H NMR (400MHz, CDCl3) δ 8.11-8.08 (m, 2H),
7.53-7.48 (m, 1H), 7.38-7.32 (m, 2H), 2.45 (s, 3H); 13C NMR (100MHz, CDCl3) δ 158.1, 139.7,
134.1, 131.4, 129.8, 128.2, 127.0, 113.8, 112.4, 83.9; HRMS calcd for C11H7N2 [M－H]+:
167.0609, found: m/z 167.0609; IR (neat) 2226, 1578, 1482, 1372, 1304, 1269, 1231 cm-1.
S4

3. NHC-promoted [3+2] cyclization of allenyl sulfone and arylidenemalononitrile
a. General procedure for NHC-promoted [3+2] cyclization of allenyl sulfone and arylidenemalononitriles
A 10 mL flame-dried test tube with a magnetic stirring bar was charged with 1a (1.2 mg, 0.003 mmol), Cs2CO3 (1.0
mg, 0.003 mmol), allenyl sulfone 2a (18 mg, 0.1 mmol), and arylidenemalononitrile 3 (0.12 mmol). The test tube
was filled with argon by the evacuation−refill process. After addition of THF (0.5 mL), the mixture was stirred at
ambient temperature until TLC monitoring showed that 2a was completely consumed. After evaporation of THF in
vacuo, the residue was purified by silica-gel column chromatography to give product 4.
b. Analytical data for product 4
2-Phenyl-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4a)
Accoding to the General Procedure, the title compound was obtained after 24 h. Silica gel column
chromatography (hexane:EtOAc = 4:1 to 2:1) gave the product as pale green oil (31 mg, 92%
yield). Rf=0.30 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.93 (m, 2H), 7.76 (t,
J = 7.6 Hz, 1H), 7.67-7.59 (m, 4H), 7.49-7.46 (m, 3H), 6.44 (d, J = 2.8 Hz, 1H), 4.67 (ddd, J =
2.8, 5.6, 8.4 Hz, 1H), 3.26 (dd, J = 5.6, 15.6 Hz, 1H), 3.20 (dd, J = 8.4, 15.6 Hz, 1H); 13C NMR
(100MHz, CDCl3) δ 142.8, 135.9, 135.0, 130.7, 129.8, 129.2, 129.1, 128.9, 126.7, 125.9, 114.5, 113.4, 69.7, 40.0,
38.2; HRMS calcd for C19H18N3O2S [M+NH4]+: 352.1120, found: m/z 352.1118; IR (neat) 2241, 1585, 1497, 1448,
1308, 1224, 1142, 1089 cm-1.
2-(4-Fluorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4b)
Accoding to the General Procedure, the title compound was obtained after 30 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 3:1) gave the product as pale green oil (30 mg,
84% yield). Rf=0.30 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.93 (m, 2H),
7.76 (tt, J = 1.2, 7.6 Hz, 1H), 7.67-7.59 (m, 4H), 7.19-7.15 (m, 2H), 6.38 (d, J = 2.8 Hz, 1H),
4.66 (ddd, J = 2.4, 5.6, 8.4 Hz, 1H), 3.26 (dd, J = 5.6, 15.2 Hz, 1H), 3.18 (dd, J = 8.8, 15.2 Hz,
1
1H); 13C NMR (100MHz, CDCl3) δ 163.9 (d, JCF = 256.5 Hz), 141.9, 135.9, 135.0, 129.9,
128.93, 128.86 (d, 3JCF = 6.7 Hz), 125.9, 125.5, 116.6 (d, 2JCF = 22.9 Hz), 114.3, 113.3, 69.7, 40.2, 38.3; HRMS calcd
for C19H17FN3O2S [M+NH4]+: 370.1026, found: m/z 370.1028; IR (neat) 2283, 1604, 1512, 1447, 1321, 1239, 1150,
1085 cm-1.
2-(4-Chlorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4c)
Accoding to the General Procedure, the title compound was obtained after 24 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 3:1) gave the product as pale green oil (34
mg, 92% yield). Rf=0.33 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.92 (m,
2H), 7.76 (t, J = 7.6 Hz, 1H), 7.67-7.63 (m, 2H), 7.56-7.53 (m, 2H), 7.46-7.44 (m, 2H), 6.44
(d, J = 2.8 Hz, 1H), 4.66 (ddd, J = 2.8, 5.6, 8.4 Hz, 1H), 3.26 (dd, J = 5.6, 15.6 Hz, 1H), 3.18
13
(dd, J = 8.4, 15.6 Hz, 1H); C NMR (100MHz, CDCl3) δ 141.7, 136.9, 135.8, 135.0, 129.9,
129.6, 128.9, 128.0, 127.6, 126.6, 114.2, 113.2, 69.7, 40.0, 38.2; HRMS calcd for C19H17ClN3O2S [M+NH4]+:
386.0730, found: m/z 386.0736; IR (neat) 2262, 1494, 1448, 1405, 1311, 1266, 1219, 1154, 1096 cm-1.
S5

2-(4-Bromophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4d)
Accoding to the General Procedure, the title compound was obtained after 8 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 3:1) gave the product as pale green solids (38
mg, 92% yield). Rf=0.33 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.92 (m,
2H), 7.77 (tt, J = 7.6, 1.2 Hz, 1H), 7.67-7.55 (m, 4H), 7.49-7.45 (m, 2H), 6.44 (d, J = 2.8 Hz,
1H), 4.66 (ddd, J = 2.8, 5.6, 8.4 Hz, 1H), 3.26 (dd, J = 5.6, 15.6 Hz, 1H), 3.18 (dd, J = 8.4, 15.6
Hz, 1H); 13C NMR (100MHz, CDCl3) δ 141.8, 135.8, 135.0, 132.5, 129.9, 128.9, 128.1, 128.0,
126.7, 125.2, 114.2, 113.2, 69.7, 39.9, 38.2; HRMS calcd for C19H17BrN3O2S [M+NH4]+: 430.0225, found: m/z
430.0226; IR (neat) 2233, 1492, 1447, 1322, 1276, 1266, 1152, 1085 cm-1. Single crystals were obtained by
recrystallization from acetone and hexane.
2-(4-Iodophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4e)
Accoding to the General Procedure, the title compound was obtained after 48 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 2:1) gave the product as gray solids (25 mg,
54% yield). Rf=0.33 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.93 (d, J = 8.0 Hz,
2H), 7.82 (d, J = 8.0 Hz, 2H), 7.76 (t, J = 8.0 Hz, 1H), 7.65 (t, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0
Hz, 2H), 6.47 (d, J = 2.8 Hz, 1H), 4.64 (ddd, J = 2.4, 5.6, 8.4 Hz, 1H), 3.25 (dd, J = 5.6, 15.6
13
Hz, 1H), 3.18 (dd, J = 8.4, 15.6 Hz, 1H); C NMR (100MHz, CDCl3) δ 142.0, 138.5, 135.8,
135.1, 129.9, 128.9, 128.6, 128.1, 126.7, 114.2, 113.2, 97.3, 69.7, 39.9, 38.2; HRMS calcd for C19H17IN3O2S
[M+NH4]+: 478.0086, found: m/z 478.0081; IR (neat) 2256, 1583, 1488, 1447, 1397, 1309, 1155, 1085, 1005 cm-1.
2-(4-Nitrophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4f)
A 10 mL flame-dried test tube with a magnetic stirring bar was charged with 1a (1.2 mg,
0.003 mmol), Cs2CO3 (1.0 mg, 0.003 mmol), allenyl sulfone 2a (18 mg, 0.1 mmol), and 3f
(24 mg, 0.12 mmol). The test tube was filled with argon by the evacuation−refill process.
After addition of THF (0.5 mL), the mixture was stirred at ambient for 12 h. To the
suspension, additional 1a (1.2 mg, 0.003 mmol) and Cs2CO3 (1.0 mg, 0.003 mmol) were
added and the mixture was stirred for 5 h. After evaporation of THF in vacuo, the residue
was purified by silica-gel column chromatography (hexane:EtOAc = 4:1 to 1:2) to give product 4f as white solids (20
mg, 53% yield). Rf=0.24 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 8.36-8.33 (m, 2H), 7.97-7.94 (m, 2H),
7.82-7.77 (m, 3H), 7.70-7.66 (m, 2H), 6.64 (d, J = 2.4 Hz, 1H), 4.71 (ddd, J = 2.8, 5.6, 8.4 Hz, 1H), 3.32 (dd, J = 5.6,
15.2 Hz, 1H), 3.21 (dd, J = 8.8, 15.2 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 148.6, 140.9, 135.9, 135.2, 135.1, 130.4,
130.0, 128.8, 127.8, 124.5, 113.9, 112.9, 69.7, 40.1, 38.2; HRMS calcd for C19H17N4O4S [M+NH4]+: 397.0971,
found: m/z 397.0968; IR (neat) 2249, 1598, 1516, 1447, 1352, 1155, 1084 cm-1.
S6

4-(Phenylsulfonyl)-2-(p-tolyl)cyclopent-2-ene-1,1-dicarbonitrile (4g)
Accoding to the General Procedure, the title compound was obtained after 20 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 2:1) gave the product as pale yellow oil (31
mg, 88% yield). Rf=0.39 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.94-7.92 (m,
2H), 7.75 (tt, J = 1.6, 7.2 Hz, 1H), 7.66-7.62 (m, 2H), 7.51-7.49 (m, 2H), 7.27-7.25 (m, 2H),
6.39 (d, J = 2.4 Hz, 1H), 4.66 (ddd, J = 2.4, 5.6, 8.4 Hz, 1H), 3.24 (dd, J = 5.2, 15.6 Hz, 1H),
3.18 (dd, J = 8.8, 15.2 Hz, 1H), 2.40 (s, 3H); 13C NMR (100MHz, CDCl3) δ 142.8, 141.1,
135.8, 134.9, 129.9, 129.8, 128.9, 126.6, 126.3, 124.7, 114.6, 113.5, 69.7, 39.9, 38.2, 21.3; HRMS calcd for
C20H20N3O2S [M+NH4]+: 366.1276, found: m/z 366.1275; IR (neat) 2260, 1509, 1447, 1309, 1152, 1085 cm-1.
2-(3-Fluorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4h)
Accoding to the General Procedure, the title compound was obtained after 31 h. Silica gel
column chromatography (hexane:EtOAc = 4:1) gave the product as pale green oil (30 mg,
85% yield). Rf=0.33 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.97-7.93 (m, 2H),
7.77 (tt, J = 1.2, 7.6 Hz, 1H), 7.68-7.62 (m, 2H), 7.48-7.39 (m, 2H), 7.32-7.16 (m, 2H), 6.45
(d, J = 2.8 Hz, 1H), 4.67 (ddd, J = 2.8, 5.6, 8.4 Hz, 1H), 3.27 (dd, J = 5.6, 15.6 Hz, 1H), 3.19
(dd, J = 8.8, 15.2 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 162.8 (d, 1JCF = 252.8 Hz), 141.7, 135.8, 135.0, 131.2 (d,
3JCF = 7.6 Hz), 131.1 (d, 3JCF = 8.6 Hz), 129.9, 128.9, 127.6, 122.5, 117.8 (d, 2JCF = 22.0 Hz), 114.2, 113.9 (d, 2JCF
=
23.8 Hz), 113.2, 69.6, 40.1, 38.2; HRMS calcd for C19H17FN3O2S [M+NH4]+: 370.1026, found: m/z 370.1021; IR
(neat) 2225, 1446, 1322, 1266, 1153, 1085 cm-1.
2-(3-Chlorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4i)
Accoding to the General Procedure, the title compound was obtained after 20 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 3:1) gave the product as pale green oil (31
mg, 84% yield). Rf=0.33 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.93 (m,
2H), 7.78 (tt, J = 1.2, 7.6 Hz, 1H), 7.70-7.64 (m, 2H), 7.55-7.40 (m, 4H), 6.45 (d, J = 2.8 Hz,
1H), 4.67 (ddd, J = 2.4, 5.2, 8.4 Hz, 1H), 3.28 (dd, J = 5.2, 15.2 Hz, 1H), 3.19 (dd, J = 8.8,
13
15.6 Hz, 1H); C NMR (100MHz, CDCl3) δ 141.6, 135.9, 135.3, 135.1, 130.9, 130.8, 130.6, 129.9, 128.9, 127.7,
126.9, 124.7, 114.2, 113.2, 69.6, 40.0, 38.2; HRMS calcd for C19H17ClN3O2S [M+NH4]+: 386.0730, found: m/z
386.0732; IR (neat) 2278, 1567, 1447, 1321, 1268, 1085 cm-1.
2-(3-Bromophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4j)
Accoding to the General Procedure, the title compound was obtained after 20 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 3:1) gave the product as pale green oil (36
mg, 87% yield). Rf=0.32 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.94 (d, J =
7.2 Hz, 2H), 7.77 (t, J = 7.2 Hz, 1H), 7.70-7.55 (m, 5H), 7.36 (t, J = 8.0 Hz, 1H), 6.45 (d, J
= 2.4 Hz, 1H), 4.67 (ddd, J = 2.4, 5.6, 8.4 Hz, 1H), 3.27 (dd, J = 5.2, 15.2 Hz, 1H), 3.19 (dd,
J = 8.8, 15.6 Hz, 1H); 13C NMR (100MHz, CDCl3) δ 141.5, 135.9, 135.1, 133.7, 131.2, 130.8, 129.9, 129.8, 128.9,
127.7, 125.1, 123.3, 114.1, 113.1, 69.6, 40.0, 38.2; HRMS calcd for C19H17BrN3O2S [M+NH4]+: 430.0225, found:
m/z 430.0223; IR (neat) 2229, 1560, 1447, 1322, 1085 cm-1.
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2-(3-Iodophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4k)
Accoding to the General Procedure, the title compound was obtained after 46 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 2:1) gave the product as pale yellow oil (42
mg, 91% yield). Rf=0.32 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.93 (m,
2H), 7.89-7.87 (m, 1H), 7.82-7.76 (m, 2H), 7.68-7.58 (m, 2H), 7.36 (t, J = 8.0 Hz, 1H), 6.44
(d, J = 2.4 Hz, 1H), 4.66 (ddd, J = 2.8, 5.2, 8.4 Hz, 1H), 3.27 (dd, J = 5.6, 15.6 Hz, 1H), 3.18
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(dd, J = 8.8, 15.2 Hz, 1H); C NMR (100MHz, CDCl3) δ 141.4, 139.6, 135.9, 135.7, 135.1, 131.2, 130.8, 129.9,
128.9, 127.5, 125.6, 114.1, 113.1, 94.9, 69.6, 40.0, 38.3; HRMS calcd for C19H17IN3O2S [M+NH4]+: 478.0086, found:
m/z 478.0087; IR (neat) 2249, 1554, 1447, 1309, 1151, 1082 cm-1.
4-(Phenylsulfonyl)-2-(m-tolyl)cyclopent-2-ene-1,1-dicarbonitrile (4l)
Accoding to the General Procedure, the title compound was obtained after 19 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 1:1) gave the product as pale green oil
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(31 mg, 88% yield). Rf=0.32 (hexane:EtOAc = 2:1); H NMR (400MHz, CDCl3) δ 7.95-
7.93 (m, 2H), 7.75 (tt, J = 1.2, 7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 2H), 7.42-7.25 (m, 4H), 6.41
(d, J = 2.4 Hz, 1H), 4.66 (ddd, J = 2.4, 5.6, 8.4 Hz, 1H), 3.24 (dd, J = 5.6, 15.2 Hz, 1H),
3.18 (dd, J = 8.8, 15.6 Hz, 1H), 2.41 (s, 3H); 13C NMR (100MHz, CDCl3) δ 143.0, 139.1, 135.9, 134.9, 131.5, 129.8,
129.10, 129.08, 128.9, 127.3, 125.6, 123.8, 114.5, 113.5, 69.7, 40.0, 38.3, 21.4; HRMS calcd for C20H20N3O2S
[M+NH4]+: 366.1276, found: m/z 366.1272; IR (neat) 2283, 1585, 1448, 1322, 1267, 1153, 1086 cm-1.
2-(3-Methoxyphenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4m)
Accoding to the General Procedure, the title compound was obtained after 19 h. Silica gel
column chromatography (hexane:EtOAc = 3:1) gave the product as pale yellow oil (35
mg, 95% yield). Rf=0.26 (hexane:EtOAc = 2:1); 1H NMR (400MHz, CDCl3) δ 7.95-7.92
(m, 2H), 7.75 (tt, J = 1.2, 7.2 Hz, 1H), 7.64 (t, J = 7.2 Hz, 2H), 7.38 (t, J = 8.0 Hz, 1H),
7.20-7.19 (m, 1H), 7.09-7.08 (m, 1H), 7.02-6.99 (m, 1H), 6.42 (d, J = 2.8 Hz, 1H), 4.66
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(ddd, J = 2.4, 5.6, 8.0 Hz, 1H), 3.85 (s, 3H), 3.25 (dd, J = 5.6, 15.6 Hz, 1H), 3.18 (dd, J = 8.4, 15.2 Hz, 1H); C
NMR (100MHz, CDCl3) δ 159.9, 142.7, 135.8, 135.0, 130.4, 130.3, 129.8, 128.9, 126.3, 119.0, 116.2, 114.5, 113.4,
112.3, 69.6, 55.3, 40.1, 38.2; HRMS calcd for C20H20N3O3S [M+NH4]+: 382.1225, found: m/z 382.1223; IR (neat)
2256, 1601, 1580, 1491, 1447, 1319, 1217, 1151, 1085, 1038 cm-1.
2-(Naphthalen-2-yl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarbonitrile (4n)
Accoding to the General Procedure, the title compound was obtained after 45 h. Silica gel
column chromatography (hexane:EtOAc = 4:1 to 1:3) gave the product as pale yellow solids
(28 mg, 73% yield). Rf=0.29 (hexane:EtOAc = 2:1); 1H NMR (400MHz, acetone–d6) δ 8.29
(d, J = 1.6 Hz, 1H), 8.06-7.90 (m, 6H), 7.83 (tt, J = 1.6, 7.6 Hz, 1H), 7.73 (t, J = 7.6 Hz,
2H), 7.65-7.60 (m, 2H), 6.91 (d, J = 2.8 Hz, 1H), 5.15 (ddd, J = 2.8, 4.4, 8.8 Hz, 1H), 3.57
(dd, J = 8.8, 15.6 Hz, 1H), 3.43 (dd, J = 4.4, 15.6 Hz, 1H); 13C NMR (100MHz, acetone-
d6) δ 142.8, 138.1, 135.7, 134.9, 134.0, 130.8, 130.2, 130.1, 129.7, 129.3, 128.8, 128.4, 128.2, 127.4, 124.9, 116.3,
115.5, 71.0, 41.2, 39.1; HRMS calcd for C23H20N3O2S [M+NH4]+: 402.1276, found: m/z 402.1273; IR (neat) 2229,
1315, 1146 cm-1.
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4. NMR spectra
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5. Single Crystal X-Ray Analysis of 4d
A colorless prism crystal having approximate dimensions of 0.500 x 0.500 x 0.300 mm was mounted on a glass
fiber. All measurements were made on a Rigaku RAXIS RAPID imaging plate area detector with graphite
monochromated Mo-Kα radiation. The data were collected at a temperature of 23 + 1 °C to a maximum 2θ value of
54.9°. The structures were solved by direct method (SIR-92)2, and hydrogen atoms were placed at the calculation. A
full-matrix least-squares technique was using with anisotropic thermal parameters for non-hydrogen atoms and riding
model for hydrogen atoms. All calculations were performed using the Crystal Structure3,4 crystallographic software
package.
4d; C19H13BrN2O2S, M=413.29, monoclinic, space group P21/n (#14), a=10.2777(8), b=10.2776(10), c=16.4290(12)
Å, V=1732.3(2) Å3, Dc=1.585 gcm-3, Z=4, R=0.0514 for 2543 observed reflections (I > 2.00σ(I)), Rw=0.0644.
Deposition number CCDC-1485660 for compound 4d. Free copies of the data can be obtained via
http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge, CB2 1EZ, UK; Fax: +44 1223 336033; e-mail: deposit@ccdc.cam.ac.uk).
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SIR92: A. Altomare, G. Cascarano, C. Giacovazzo, and A. Guagliardi, J. Appl. Cryst., 1993, 26, 343.
CrystalStructure 4.2.1: Crystal Structure Analysis Package, Rigaku Corporation (2000-2016). Tokyo 196-8666,
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Japan.
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CRYSTALS Issue 11: J. R. Carruthers, J. S. Rollett, P. W. Betteridge, D. Kinna, L. Pearce, A. Larsen, and E.
Gabe, Chemical Crystallography Laboratory, Oxford, UK. (1999)
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