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S1
Supporting Information
FeCl3-Catalyzed Cascade Reaction: An Efficient Approach to
Functionalized Coumarin Derivatives
Xinwei He, Zhenglei Yan, Xiaoqian Hu, Yin Zuo, Chang Jiang, Lei Jin,
Yongjia Shang*
Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecule-Based
Materials, College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, P.R. China
E-mail: [email protected]
Contents: pages
Table of
contents ································································································ S1
Experimental
section··························································································· S2 1H and 13C NMR spectra data of all products ················································· S3-S9 1H and 13C NMR spectra of all products ························································· S10-S29
Crystal data and structure refinement for 3b···················································· S30-S33
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S2
Experimental Section
General comments 1H NMR spectra were recorded on a 300 MHz instrument. Chemical shifts for 1H NMR were reported as δ (parts per million) relative to the signal of CHCl3 at 7.26 (s) ppm. Chemical shifts for 13C NMR were reported as δ (parts per million) relative to the CDCl3 triplet at 76.0 ppm. HRMS were obtained using (ESI) mass spectrometer (TOF). IR spectra of liquid compounds were recorded as neat, whereas KBr plates were used for solid compounds. All solvents were purified and dried by following standard procedures unless otherwise stated.
General procedure for the synthesis of substituted coumarin derivatives 3. To a stirred solution of salicyladehyde 1 (1 mmol) and the activated methylene compounds 2 (1.2 mmol) in ethanol (3 mL) was added anhydrous FeCl3 (0.05mmol). The mixture was heated in an oil bath at 80 oC for 24 h and cooled down to room temperature. The solvent was removed under vacuum, and the residue was directly purified by flash column chromatography on silica gel (200-300 mesh) with ethyl acetate and petroleum ester (1:6-1:8, v/v) as eluting solvent to afford the product 3.
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S3
1H and 13C NMR spectra data of all products
O O
CN
2-Oxo-2H-chromene-3-carbonitrile (3a) [1]
White solid; Yield: 123 mg, (72%); mp 175-176 oC.
IR (KBr) v: 3107, 3072, 3045, 2924, 2229, 1774, 1728, 1604, 1560, 1446, 1369, 1288, 1257, 1188,
1149, 1051, 972, 763 cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.22 (s, 1H, CH), 7.67 (t, J = 7.5 Hz, 1H, ArH), 7.56 (d, J = 7.4
Hz, 1H, ArH), 7.35 (d, J = 4.6 Hz, 2H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 151.9, 135.6, 129.3, 125.8, 117.5, 113.5, 106.8, 101.0 ppm.
HRMS (ESI) calcd for C10H5NO2 (M+H+) 172.0398, found 172.0393.
O O
CNCl
6-Chloro-2-oxo-2H-chromene-3-carbonitrile (3b) [2]
White solid; Yield: 153 mg (75%); mp 194-195 oC.
IR (KBr) v: 3068, 3037, 2378, 2310, 2243, 1735, 1612, 1562, 1479, 1415, 1359, 1247, 1186, 1051,
939, 881, 837, 765, 682 cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.20 (s, 1H, CH), 7.65 (t, J = 8.7 Hz, 1H, ArH), 7.59 (s, 1H, ArH),
7.35 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 149.5, 134.3, 127.4, 127.2, 117.9, 117.2 ppm.
HRMS (ESI) calcd for C10H4ClNO2 (M+H+) 206.0009, found 206.0010.
O O
CNBr
6-Bromo-2-oxo-2H-chromene-3-carbonitrile (3c) [1]
White solid; Yield: 186 mg (75%); mp 196-197 oC.
IR (KBr) v: 3089, 3068, 2972, 2897, 2372, 1753, 1705, 1616, 1598, 1558, 1471, 1411, 1352, 1290,
1240, 1209, 1134, 1070, 1024, 995, 837, 794, 653 cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.19 (s, 1H, CH), 7.78 (d, J = 9.0 Hz, 1H, ArH), 7.59 (s, 1H, ArH),
7.28 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 149.4, 137.1, 130.2, 118.0, 117.4 ppm.
HRMS (ESI) calcd for C10H4BrNO2 (M+H+) 249.9503, found 249.9503.
O O
CN(H3C)3
(CH3)3 6,8-Di-tert-butyl-2-oxo-2H-chromene-3-carbonitrile (3d) [3]
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S4
White solid; Yield: 263 mg (93%); mp 151-152 oC.
IR (KBr) v:2970, 2910, 2875, 2320, 2233, 1745, 1614, 1577, 1465, 1452, 1394, 1369, 1330, 1244,
1201, 1176, 1041, 945, 761 cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.24 (s, 1H, CH), 7.74 (s, 1H, ArH), 7.36 (s, 1H, ArH), 1.48 (s,
9H, t-Bu), 1.35 (s, 9H, t-Bu) ppm. 13C NMR (75MHz, CDCl3) δ: 152.3, 147.3, 137.3, 130.3, 122.9, 116.3, 113.0, 100.9, 34.3, 33.9,
30.3, 28.8 ppm.
HRMS (ESI) calcd for C18H21NO2 (M+H+) 284.1650, found 284.1648.
7-Methoxy-2-oxo-2H-chromene-3-carbonitrile (3e) [4]
Yellow solid; Yield: 160 mg (80%); mp 127-128 oC.
IR (KBr) v: 3053, 2956, 2922, 2848, 2372, 2229, 1751, 1608, 1560, 1506, 1473, 1444, 1381,
1294, 1215, 1172, 1114, 1020, 829, 798 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.49 (s, 1H, CH), 7.48 (d, J = 8.4 Hz, 1H, ArH), 6.87 (d, J = 8.7
Hz, 1H, ArH), 6.80 (s, 1H, ArH), 3.89 (s, 3H, OCH3) ppm. 13C NMR (75MHz, CDCl3) δ: 165.2, 163.5, 151.3, 148.9, 130.6, 130.2, 114.4, 113.6, 111.6, 101.1,
101.0, 100.3, 55.9 ppm.
HRMS (ESI) calcd for C11H7NO3 (M+H+) 202.0504, found 202.0504.
Ethyl 2-oxo-2H-chromene-3-carboxylate (3f) [5]
White solid; Yield: 207 mg (95%); mp 95-96 oC.
IR (KBr) v: 3469, 3062, 2978, 1776, 1766, 1606, 1564, 1450, 1375, 1296, 1247, 1207, 1132, 1033,
985, 962, 920, 866, 775 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.37 (s, 1H, CH), 7.49 (d, J = 7.3 Hz, 2H, ArH), 7.11-7.19 (m, 2H,
ArH), 4.23 (q, J = 6.7 Hz, 2H, CH2), 1.23 (t, J = 6.9 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 156.5, 154.8, 134.3, 129.6, 124.8, 117.8, 117.6, 116.4, 61.7,
14.1 ppm.
HRMS (ESI) calcd for C12H10O4 (M+H+) 219.0657, found 219.0657.
Ethyl 6-chloro-2-oxo-2H-chromene-3-carboxylate (3g) [6]
White solid; Yield: 224 mg (89%); mp 173-174 oC.
IR (KBr) v: 3070, 2976, 2899, 2372, 1755, 1705, 1616, 1560, 1473, 1415, 1367, 1290, 1244, 1211,
1083, 1024, 997, 840, 794, 663, 605 cm-1.
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S5
1H NMR (300 MHz, CDCl3) δ: 8.43 (s, 1H, CH), 7.60 (s, 1H, ArH), 7.26-7.33 (m, 2H, ArH), 4.43
(q, J = 6.9 Hz, 2H, CH2), 1.41 (t, J = 6.9 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 146.2, 133.2, 127.5, 117.9, 117.4, 61.3, 13.3 ppm.
HRMS (ESI) calcd for C12H9ClO4 (M+H+) 253.0267, found 253.0267.
Ethyl 6-bromo-2-oxo-2H-chromene-3-carboxylate (3h) [7]
White solid; Yield: 250 mg (85%); mp 164-166 oC.
IR (KBr) v: 3070, 2972, 2899, 2360, 1753, 1705, 1616, 1598, 1558, 1477, 1411, 1367, 1290, 1242,
1211, 1024, 995, 837, 794 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.44 (s, 1H, CH), 7.24 (s, 1H, ArH), 7.70-7.78 (m, 2H, ArH), 4.43
(q, J = 7.0 Hz, 2H, CH2), 1.41 (t, J = 7.2 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 161.7, 155.1, 153.0, 149.6, 146.2, 137.2, 136.0, 130.6, 130.5, 118.5,
118.4, 118.2, 117.6, 116.4, 61.3, 13.3 ppm.
HRMS (ESI) calcd for C12H9BrO4 (M+H+) 296.9762, found 296.9765.
Ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate (3i) [8]
Yellow solid; Yield: 198 mg (80%); 132-134 oC.
IR (KBr) v: 3053, 2985, 2926, 2848, 2229, 1753, 1726, 1714, 1620, 1606, 1558, 1506, 1381,
1294, 1217, 1172, 1118, 1031, 829, 798, 761 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.48 (s, 1H, CH), 7.47 (d, J = 8.7 Hz, 1H, ArH), 6.87 (d, J = 8.7
Hz, 1H, ArH), 6.78 (s, 1H, ArH), 4.38 (q, J = 7.0 Hz, 2H, CH2), 3.87 (s, 3H, OCH3), 1.37 (t, J =
7.1 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 164.2, 162.5, 156.6, 156.2, 148.1, 129.8, 113.1, 112.7, 110.7, 99.4,
60.8, 55.1, 28.8, 13.4 ppm.
HRMS (ESI) calcd for C13H12O5 (M+H+) 249.0763, found 249.0762.
Ethyl 6-nitro-2-oxo-2H-chromene-3-carboxylate (3j) [9]
White solid; Yield: 199 mg (70%); mp 203-204 oC.
IR (KBr) v: 3088, 3055, 2993, 2922, 2372, 1780, 1757, 1691, 1618, 1570, 1527, 1497, 1348,
1305, 1257, 1219, 1095, 1018, 985, 848, 794, 752 cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.56 (s, 1H, CH), 8.48 (d, J = 6.9 Hz, 1H, ArH), 7.48 (d, J = 9.0
Hz, 1H, ArH), 4.44 (q, J = 6.9 Hz, 2H, CH2), 1.41 (t, J = 6.9 Hz, 3H, CH3) ppm.
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S6
13C NMR (75MHz, CDCl3) δ: 146.0, 127.7, 124.3, 117.2, 61.6, 13.3 ppm.
HRMS (ESI) calcd for C12H9NO6 (M+Na+) 286.0322, found 286.0324.
O O
O
O
N
Ethyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate (3k) [10]
Pale brown solid; Yield: 231 mg (80%); mp 172-173 oC.
IR (KBr) v: 3525, 3446, 3354, 2976, 2922, 2872, 2700, 2376, 2322, 2220, 1732, 1699, 1622,
1589, 1514, 1477, 1446, 1423, 1354, 1311, 1222, 1186, 1141, 1103, 1028, 819, 792, 684, 638
cm-1.
1H NMR (300 MHz, CDCl3) δ: 8.38 (s, 1H, CH), 7.32 (d, J = 8.9 Hz, 1H, ArH), 6.57 (d, J = 8.7
Hz, 1H, ArH), 6.40 (s, 1H, ArH), 4.35 (q, J = 6.9 Hz, 2H, OCH2), 3.42 (q, J = 6.8 Hz, 2H, NCH2),
1.35 (t, J = 7.0 Hz, 3H, CH3), 1.20 (t, J = 6.7 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 163.3, 157.5, 152.0, 149.7, 148.2, 130.1, 129.8, 109.2, 108.6, 107.9,
106.7, 96.2, 95.7, 60.2, 44.3, 44.2, 13.5, 11.5 ppm.
HRMS (ESI) calcd for C16H19NO4 (M+H+) 290.1392, found 290.1393.
O O
CN
CH3
4-Methyl-2-oxo-2H-chromene-3-carbonitrile (3l) [11]
White solid; Yield: 92 mg (50%); mp 120-122 oC.
IR (KBr) v: 3344, 3226, 2962, 2922, 2850, 2378, 2349, 2320, 2204, 1720, 1602, 1564, 1450,
1386, 1261, 1226, 1085, 1022, 804, 758 cm-1.
1H NMR (300 MHz, CDCl3) δ: 7.76 (d, J = 7.8 Hz, 1H, CH), 7.48 (t, J = 7.4 Hz, 1H, ArH), 6.98
(d, J = 8.4 Hz, 1H, ArH), 6.91 (t, J = 7.4 Hz, 1H, ArH), 2.64 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.2, 156.7, 136.5, 130.7, 118.9, 118.4, 26.7 ppm.
HRMS (ESI) calcd for C11H7NO2 (M+H+) 186.0555, found 186.0556.
O O
CH3
NH2
O
4-Methyl-2-oxo-2H-chromene-3-carboxamide (3m) [12]
Pale brown solid; Yield: 83 mg (41%).
IR (KBr) v: 3523, 3435, 3263, 3078, 2983, 2918, 2351, 2320, 1778, 1716, 1606, 1566, 1446,
1386, 1367, 1267, 1184, 1151, 1070, 925, 848, 752, 704, 576, 509 cm-1. 1H NMR (300 MHz, CDCl3) δ: 7.62 (d, J = 7.8 Hz, 1H, CH), 7.54 (t, J = 7.5 Hz, 1H, ArH), 7.33
(t, J = 7.7 Hz, 1H, ArH), 7.27 (d, J = 7.3 Hz, 1H, ArH), 6.31(s, 2H, NH2), 2.45 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 165.3, 130.9, 123.6, 123.3, 116.2, 114.2, 17.7 ppm.
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S7
HRMS (ESI) calcd for C11H9NO3 (M+H+) 204.0660, found 204.0661.
O O
NH2
O
N
7-(Diethylamino)-2-oxo-2H-chromene-3-carboxamide (3n) [13]
Yellow solid; Yield: 150 mg (58%).
IR (KBr) v: 3392, 3319, 3151, 2964, 2926, 2868, 2351, 1691, 1666, 1620, 1566, 1514, 1423,
1355, 1251, 1188, 1136, 1080, 974, 806, 578 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.69 (s, 1H, CH), 8.55 (s, 1H, NH2), 7.40 (d, J = 8.9 Hz, 1H, ArH),
6.43 (d, J = 7.5 Hz, 1H, ArH), 6.48 (s, 1H, ArH), 5.88 (s, 2H, NH2), 3.46 (q, J = 6.9 Hz, 4H, CH2),
1.23 (t, J = 6.9 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 164.1, 161.6, 157.0, 151.9, 147.9, 130.4, 109.1, 108.7, 107.4, 95.6,
44.2, 11.5 ppm.
HRMS (ESI) calcd for C14H16N2O3 (M+H+) 261.1239, found 261.1239.
3-Oxo-3H-benzo[f]chromene-2-carbonitrile (3o) [14]
White solid; Yield: 165 mg (75%); mp 96-97 oC.
IR (KBr) v: 2954, 2924, 2852, 2376, 2349, 2310, 1743, 1629, 1602, 1514, 1465, 1379, 1278,
1217, 1172, 960, 844, 813, 742, 713 cm-1. 1H NMR (300 MHz, CDCl3) δ: 9.31 (s, 1H, CH), 8.31 (d, J = 8.1 Hz, 1H, ArH), 8.09 (d, J = 9.0
Hz, 1H, ArH), 7.91 (d, J = 7.8 Hz, 1H, ArH), 7.74 (d, J = 7.2 Hz, 1H, ArH), 7.62 (d, J = 6.9 Hz,
1H, ArH), 7.46 (d, J = 8.7 Hz, 1H, ArH) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 156.0, 155.0, 143.6, 135.2, 129.3, 128.9, 128.5, 128.3, 128.2,
125.7, 120.6, 115.7, 115.5, 111.3, 28.8 ppm.
HRMS (ESI) calcd for C14H7NO2 (M+H+) 222.0555, found 222.0553.
Ethyl 3-oxo-3H-benzo[f]chromene-2-carboxylate (3p) [15]
Yellow solid; Yield: 246 mg (92%); mp 115-117 oC.
IR (KBr) v: 3080, 2974, 2902, 2349, 1745, 1697, 1627, 1604, 1568, 1517, 1463, 1396, 1296,
1259, 1217, 1124, 1095, 825, 798, 742 cm-1. 1H NMR (300 MHz, CDCl3) δ: 9.30 (s, 1H, CH), 8.30 (d, J = 8.4 Hz, 1H, ArH), 8.09 (d, J = 9.0
Hz, 1H, ArH), 7.92 (d, J = 7.8 Hz, 1H, ArH), 7.74 (t, J = 7.5 Hz, 1H, ArH), 7.60 (t, J = 7.5 Hz,
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1H, ArH), 7.44 (d, J = 9.0 Hz, 1H, ArH), 4.47 (q, J = 10.5 Hz, 2H, CH2), 1.45 (t, J = 10.5 Hz, 3H,
CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.7, 155.0, 143.6, 135.2, 129.3, 128.5, 128.3, 128.2, 125.6, 120.6,
115.7, 115.5, 111.4, 61.2, 13.4 ppm.
HRMS (ESI) calcd for C16H12O4 (M+H+) 269.0814, found 269.0813.
O O
O
O
N
Methyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate (3q)[16]
Yellow solid; Yield: 233 mg (85%); mp 174-175 oC.
IR (KBr) v:3425, 3118, 2966, 2924, 2870, 1724, 1664, 1614, 1570, 1508, 1477, 1423, 1361, 1344,
1274, 1215, 1188, 1138, 1078, 817, 759, 621 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.45 (s, 1H, CH), 7.35 (d, J = 9.0 Hz, 1H, ArH), 6.61 (d, J = 9.0
Hz, 1H, ArH), 6.46 (s, 1H, ArH), 3.91 (s, 3H, CH3), 3.45 (q, J = 6.8 Hz, 4H, NCH2), 1.23 (t, J =
4.6 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 163.5, 157.2, 152.0, 148.8, 130.2, 108.7, 106.8, 95.8, 51.5, 44.2,
28.8, 11.5 ppm.
HRMS (ESI) calcd for C15H17NO4 (M+H+) 276.1236, found 276.1236.
O O
O
Br
3-Acetyl-6-bromo-2H-chromen-2-one (3r) [17]
White solid; Yield: 140 mg (53%); mp 281-282 oC.
IR (KBr) v: 2962, 2922, 2378, 2351, 2310, 1687, 1625, 1566, 1508, 1489, 1423, 1355, 1321,
1267, 1234, 1213, 1076, 1020, 813, 794 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.14 (s, 1H, CH), 7.57 (d, J = 8.7 Hz, 1H, ArH), 7.35 (s, 1H, ArH),
6.95 (s, 1H, ArH), 2.50 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 172.8, 162.5, 148.4, 132.7, 132.3, 125.2, 118.5, 117.2, 116.9, 112.4,
21.7 ppm.
HRMS (ESI) calcd for C11H7BrO3 (M+H+) 266.9657, found 266.9655.
O O
O
N
3-Acetyl-7-(diethylamino)-2H-chromen-2-one (3s) [18]
Yellow solid; Yield: 98 mg (38%).
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IR (KBr) v: 3086, 2976, 2933, 2872, 2719, 2351, 2220, 1753, 1701, 1616, 1583, 1512, 1454,
1417, 1355, 1311, 1220, 1201, 1134, 1080, 1016, 970, 837, 796, 692 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.44 (s, 1H, CH), 7.39 (d, J = 7.5 Hz, 1H, ArH), 7.25 (d, J = 7.5
Hz, 1H, ArH), 6.61 (s, 1H, ArH) 3.45 (q, J = 6.7 Hz, 4H, NCH2), 2.69 (s, 3H, CH3), 1.23 (t, J =
6.9 Hz, 6H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 159.9, 152.1, 147.0, 131.0, 126.7, 116.2, 108.9, 95.7, 44.2, 11.5
ppm.
HRMS (ESI) calcd for C15H17NO3 (M+H+) 260.1287, found 260.1287.
O
O
O
O2N
O
Ethyl 2-ethoxy-2-methyl-6-nitro-2H-chromene-3-carboxylate (3t)
Faint yellow solid; Yield: 291 mg (95%); mp 76-77 oC.
IR (KBr) v: 3089, 2981, 2939, 2906, 2351, 2310, 1942, 1716, 1618, 1577, 1521, 1477, 1373,
1344, 1273, 1215, 1161, 1095, 1043, 948, 885, 831, 750, 719 cm-1. 1H NMR (300 MHz, CDCl3) δ: 8.20 (d, J = 2.5 Hz, 1H, ArH), 8.17 (s, 1H, ArH), 7.70 (s, 1H, CH),
7.02 (d, J = 8.5 Hz, 1H, ArH), 4.32 (q, J = 7.1 Hz, 2H, CH2), 3.54 (q, J = 7.0 Hz, 2H, CH2), 1.98
(s, 3H, CH3), 1.37 (t, J = 7.1 Hz, 3H, CH3), 1.13 (t, J = 7.0 Hz, 3H, CH3) ppm. 13C NMR (75MHz, CDCl3) δ: 162.8, 157.7, 140.9, 132.6, 126.5, 125.9, 123.5, 117.5, 115.6, 101.9,
60.4, 58.0, 25.2, 14.2, 13.1 ppm.
HRMS (ESI) calcd for C15H17NO6 (M+H+) 308.1134, found 308.1134.
References
[1] Augustine, J. K.; Ramappa, B.; Boodappa, C.; Bombrun, A. Tetrahedron Lett. 2012, 53, 4422-4425.
[2] Yuan, H.-J.; Wang, M.; Liu, Y.-J.; Wang, L.-L. Liu, J.; Liu, Q. Chem. Eur. J. 2010, 16, 13450-13457.
[3] Fringuelli, F.; Piermatti, O.; Pizzo, F. Synthesis 2003, 2331-2334.
[4] Valizadeh, H.; Mahmoodian, M.; Gholipour, H. J. Heterocyclic Chem. 2011, 48, 799-802.
[5] Diaz, U.; Garcia, T.; Velty, A.; Corma, A. Chem. Eur. J. 2012, 18, 8659-8672.
[6] Liu, J.-B.; Wu, F.-Y.; Zhao, L.-Z.; Zhao, Z.-B.; Wang, M.; Lei, S.-L. Chen, L.-J. Food Chem. 2012, 135,
2872-2878.
[7] Starcevic, S.; Turk, S.; Cesar, J.; Gobec, S.; Brozic, P.; Lanisnik Rizner, T. J. Med. Chem. 2011, 54, 248-261.
[8] Robert, S.; Bertolla, C.; Masereel, B.; Dogne, J.-M.; Pochet, L. J. Med. Chem. 2008, 51, 3077-3080.
[9] Martinez-Martinez, F. J.; Razo-Hernandez, R. S.; Peraza-Campos, A. L.; Cano, D. J.; Gomez-Sandoval, Z.;
Villanueva-Garcia, M.; Sumaya-Martinez, M. Molecules 2012, 17, 14882-14898.
[10] Kim, T.-H.; Swager, T. M. Angew. Chem, Int. Ed. 2003, 42, 4803-4806.
[11] Ranjith, C.; Vijayan, K. K.; Paul, N. Asian J. Chem. 2011, 23, 235-238.
[12] Jana, R.; Partridge, J. J.; Tunge, J. A. Angew. Chem, Int. Ed. 2011, 50, 5157-5161.
[13] Takechi, H.; Oda, Y.; Nishizono, N.i; Oda, K.; Machida, M. Chem. Pharm. Bull. 2000, 48, 1702-1710.
[14] Kumar, B. V.; Naik, H. S. B.; Girija, D.; Kumar, B. V. J. Chem. Sci. (Bangalore) 2011, 123, 615-621.
[15] Posakony, J.; Hirao, M.; Stevens, S.; Simon, J. A.; Bedalov, A. J. Med. Chem. 2004, 47, 2635-2644.
[16] Simonin, J.; Lochner, M.; Vernekar, S. K. V.; Thompson, A. J.; Lummis, S. C. R.; Hothersall, J. D.; Connolly,
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C. N. Bioorg. Med. Chem. Lett. 2012, 22, 1151-1155.
[17] Secci, D.; Carradori, S.; Bolasco, A.; Chimenti, P.; Yanez, M.; Ortuso, F.; Alcaro, S. Eur. J. Med. Chem. 2011,
46, 4846-4852.
[18] Wu, J.-S.; Sheng, R.-L.; Liu, W.-M.; Wang, P.-F.; Zhang, H.-Y.; Ma, J.-J. Tetrahedron 2012, 68, 5458-5463.
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1H and 13C NMR spectra of all products
3a O O
CN
3a
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3b O O
CNCl
3b
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3c O O
CNBr
3c
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3d
O O
CN(H3C)3
(CH3)3
3d
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3e
3e
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3f
3f
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3g
3g
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3h
3h
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3i
3i
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3j
3j
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3k
O O
O
O
N
3k
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3l O O
CN
CH3
3l
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3m O O
CH3
NH2
O
3m
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3n
O O
NH2
O
N
3n
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3o
3o
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3p
3p
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3q
O O
O
O
N
3q
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3r O O
O
Br
3r
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3s
O O
O
N
3s
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3t
O
O
O
O2N
O
3t
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Crystal data and structure refinement for 3b
X-ray Crystallography
The diffraction data for 3b were collected on a Bruker SMART APEX diffractometer using Mo K
α (λ = 0.71073 Å). The crystallographic data are listed in Table S1. The CIF deposition number:
CCDC-850126.
Table S1. Crystal data and structure refinement for 3b.
Identification code h0521_0m
Empirical formula C20 H8 Cl2 N2 O4
Formula weight 411.18
Temperature 293(2) K
Wavelength 0.71073 A
Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 9.3655(13) A alpha = 90 deg.
b = 11.4888(16) A beta = 105.226(2) deg.
c = 16.559(2) A gamma = 90 deg.
Volume 1719.2(4) A^3
Z, Calculated density 4, 1.589 Mg/m^3
Absorption coefficient 0.410 mm^-1
F(000) 832
Crystal size 0.30 x 0.25 x 0.23 mm
Theta range for data collection 2.18 to 27.55 deg.
Limiting indices -12<=h<=12, -14<=k<=14, -20<=l<=21
Reflections collected / unique 14389 / 3951 [R(int) = 0.0268]
Completeness to theta = 27.55 99.5 %
Absorption correction Semi-empirical from equivalents
Max. and min. transmission 0.9117 and 0.8870
Refinement method Full-matrix least-squares on F^2
Data / restraints / parameters 3951 / 0 / 253
Goodness-of-fit on F^2 1.000
Final R indices [I>2sigma(I)] R1 = 0.0351, wR2 = 0.0986
R indices (all data) R1 = 0.0409, wR2 = 0.1059
Largest diff. peak and hole 0.231 and -0.316 e.A^-3
Table S2. Selected Bond lengths [Å] and angles [°] for 3b.
C(1)-O(1) 1.3741(16)
C(1)-C(2) 1.3807(19)
C(1)-C(6) 1.3973(17)
C(2)-C(3) 1.376(2)
C(2)-H(2) 0.9300
C(3)-C(4) 1.395(2)
C(3)-H(3) 0.9300
C(4)-C(5) 1.372(2)
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C(4)-Cl(1) 1.7357(14)
C(5)-C(6) 1.4018(19)
C(5)-H(5) 0.9300
C(6)-C(7) 1.4285(18)
C(7)-C(8) 1.3495(18)
C(7)-H(7) 0.9300
C(8)-C(10) 1.4342(18)
C(8)-C(9) 1.4619(18)
C(9)-O(2) 1.1953(18)
C(9)-O(1) 1.3739(17)
C(10)-N(1) 1.1361(19)
C(11)-O(4) 1.3749(15)
C(11)-C(12) 1.3818(19)
C(11)-C(16) 1.3982(17)
C(12)-C(13) 1.380(2)
C(12)-H(12) 0.9300
C(13)-C(14) 1.397(2)
C(13)-H(13) 0.9300
C(14)-C(15) 1.3691(19)
C(14)-Cl(2) 1.7336(13)
C(15)-C(16) 1.4065(18)
C(15)-H(15) 0.9300
C(16)-C(17) 1.4298(18)
C(17)-C(18) 1.3469(18)
C(17)-H(17) 0.9300
C(18)-C(20) 1.4307(19)
C(18)-C(19) 1.4629(17)
C(19)-O(5) 1.2008(16)
C(19)-O(4) 1.3664(16)
C(20)-N(2) 1.137(2)
O(1)-C(1)-C(2) 117.16(11)
O(1)-C(1)-C(6) 121.19(11)
C(2)-C(1)-C(6) 121.64(12)
C(3)-C(2)-C(1) 119.24(13)
C(3)-C(2)-H(2) 120.4
C(1)-C(2)-H(2) 120.4
C(2)-C(3)-C(4) 119.72(13)
C(2)-C(3)-H(3) 120.1
C(4)-C(3)-H(3) 120.1
C(5)-C(4)-C(3) 121.49(13)
C(5)-C(4)-Cl(1) 120.29(11)
C(3)-C(4)-Cl(1) 118.20(11)
C(4)-C(5)-C(6) 119.25(12)
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C(4)-C(5)-H(5) 120.4
C(6)-C(5)-H(5) 120.4
C(1)-C(6)-C(5) 118.65(12)
C(1)-C(6)-C(7) 117.91(12)
C(5)-C(6)-C(7) 123.41(12)
C(8)-C(7)-C(6) 120.16(12)
C(8)-C(7)-H(7) 119.9
C(6)-C(7)-H(7) 119.9
C(7)-C(8)-C(10) 121.59(12)
C(7)-C(8)-C(9) 121.90(12)
C(10)-C(8)-C(9) 116.49(12)
O(2)-C(9)-O(1) 118.21(13)
O(2)-C(9)-C(8) 125.77(13)
O(1)-C(9)-C(8) 116.01(12)
N(1)-C(10)-C(8) 178.06(16)
O(4)-C(11)-C(12) 117.27(11)
O(4)-C(11)-C(16) 120.95(11)
C(12)-C(11)-C(16) 121.78(12)
C(13)-C(12)-C(11) 118.89(13)
C(13)-C(12)-H(12) 120.6
C(11)-C(12)-H(12) 120.6
C(12)-C(13)-C(14) 119.95(13)
C(12)-C(13)-H(13) 120.0
C(14)-C(13)-H(13) 120.0
C(15)-C(14)-C(13) 121.50(12)
C(15)-C(14)-Cl(2) 119.99(11)
C(13)-C(14)-Cl(2) 118.51(11)
C(14)-C(15)-C(16) 119.19(12)
C(14)-C(15)-H(15) 120.4
C(16)-C(15)-H(15) 120.4
C(11)-C(16)-C(15) 118.67(12)
C(11)-C(16)-C(17) 118.13(11)
C(15)-C(16)-C(17) 123.20(12)
C(18)-C(17)-C(16) 119.96(12)
C(18)-C(17)-H(17) 120.0
C(16)-C(17)-H(17) 120.0
C(17)-C(18)-C(20) 122.00(12)
C(17)-C(18)-C(19) 121.87(12)
C(20)-C(18)-C(19) 116.09(11)
O(5)-C(19)-O(4) 118.23(12)
O(5)-C(19)-C(18) 125.50(13)
O(4)-C(19)-C(18) 116.28(11)
N(2)-C(20)-C(18) 178.83(18)
C(1)-O(1)-C(9) 122.58(10)
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C(19)-O(4)-C(11) 122.73(10)