10.1002/ejoc.202001072
European Journal of Organic Chemistry
FULL PAPER
(101 MHz, CDCl3): δ = 162.7, 161.9, 158.9, 158.7, 158.6, 139.8,
136.6, 131.5, 129.3, 128.9, 127.5, 126.8, 125.0, 120.8, 113.4,
98.3, 96.9, 55.8, 55.6, 55.4 ppm. HR-MS (ESI): calculated m/z
(45.0 mg, 93.2 μmol, 93%) after column chromatography (SiO2
hexane/EtOAc, 30:1, Rf = 0.22 (hexane/EtOAc, 10:1)). H-NMR
1
(400 MHz, CDCl3): δ = 7.72 (t, J = 1.7 Hz, 1H), 7.70 – 7.65 (m,
4H), 7.60 (d, J = 1.7 Hz, 2H), 7.50 – 7.44 (m, 4H), 7.41 – 7.34
(m, 2H), 7.34 – 7.26 (m, 2H), 7.21 (dd, J = 8.1, 1.3 Hz, 1H), 7.16
(td, J = 7.4, 1.4 Hz, 1H), 7.09 (s, 1H), 6.54 (d, J = 2.4 Hz, 1H),
6.25 (d, J = 2.5 Hz, 1H), 3.85 (s, 3H), 3.35 (s, 3H) ppm. 13C{1H}-
NMR (101 MHz, CDCl3): δ = 162.9, 162.1, 158.9, 158.7, 145.2,
141.54, 141.51, 140.2, 131.2, 129.5, 129.2, 128.9, 128.3, 127.5,
127.4, 125.1, 124.7, 124.4, 120.9, 113.3, 98.4, 97.0, 55.8,
+
for C23H21O4 ([M]+): 361.1434; found 361.1438. FTIR (ATR,
neat): 휈̃ = 3004, 2962, 2901, 2829, 1605, 1572, 1509, 1482,
1460, 1439, 1417, 1361, 1335, 1251, 1216, 1189, 1174, 1159,
1134, 1083, 1018, 938, 863, 794, 774, 758, 728, 681, 660, 628,
579, 553, 533, 516 cm-1.
11-(4-chlorophenyl)-1,3-dimethoxydibenzo[b,f]oxepine 13d:
Using 2 mol% of precatalyst C, and following the general
procedure, compound 13d was isolated as a white solid
(35.6 mg, 97.7 μmol, 98%) after column chromatography (SiO2,
hexane/EtOAc, 30:1, Rf = 0.17). 1H-NMR (400 MHz, CDCl3):
δ = 7.35 – 7.23 (m, 6H), 7.22 – 7.10 (m, 2H), 6.93 (s, 1H), 6.51
(d, J = 2.4 Hz, 1H), 6.23 (d, J = 2.3 Hz, 1H), 3.84 (s, 3H), 3.35 (s,
3H) ppm. 13C{1H}-NMR (101 MHz, CDCl3): δ = 162.8, 162.1,
158.7, 158.6, 142.6, 139.2, 132.3, 131.0, 129.4, 129.3, 128.3,
128.1, 127.7, 125.1, 120.9, 112.8, 98.4, 96.8, 55.7, 55.6 ppm.
+
55.7 ppm. HR-MS (ESI): calculated m/z for C34H27O3 ([M+H]+):
483.1955; found 483.1963. FTIR (ATR, neat): 휈̃ = 3057, 3029,
3008, 2958, 2934, 2838, 1607, 1565, 1485, 1453, 1434, 1415,
1353, 1326, 1287, 1263, 1234, 1212, 1193, 1151, 1131, 1107,
1087, 1046, 1027, 986, 936, 876, 848, 827, 757, 715, 695, 670,
644, 611, 563, 521 cm-1.
6-(4-methoxyphenyl)-[1,3]dioxolo[4',5':5,6]benzo[1,2-b]
benzo[f]oxepine 13h: Using 2 mol% of precatalyst C and
following the general procedure, compound 13h was isolated as
+
HR-MS (EI): calculated m/z for C22H18ClO3 ([M]+): 364.0861;
found 364.0862. FTIR (ATR, neat): 휈̃ = 2998, 2963, 2933, 2840,
1604, 1568, 1487, 1461, 1434, 1415, 1357, 1336, 1290, 1248,
1215, 1196, 1158, 1134, 1090, 1047, 1014, 985, 954, 932, 884,
861, 822, 771, 759, 742, 720, 675, 630 cm-1.
a colourless oil (25.5 mg, 74.0 μmol, 74%) after column
chromatography (SiO2, hexane/EtOAc, 30:1, Rf = 0.13). 1H-NMR
(400 MHz, CDCl3): δ = 7.42 – 7.35 (m, 2H), 7.31 – 7.24 (m, 3H),
7.19 – 7.13 (m, 1H), 6.97 – 6.90 (m, 2H), 6.77 (s, 1H), 6.53 (d, J
= 8.3 Hz, 1H), 6.46 (d, J = 8.4 Hz, 1H), 6.07 (s, 2H), 3.86 (s,
3H) ppm. 13C{1H}-NMR (101 MHz, CDCl3): δ = 159.5, 157.5,
150.2, 141.9, 141.8, 139.2, 135.4, 131.1, 130.3, 129.7, 129.1,
128.0, 125.8, 125.2, 123.5, 121.1, 113.8, 104.9, 102.3, 55.5 ppm.
1,3-dimethoxy-11-(phenanthren-9-yl)dibenzo[b,f]oxepine
13e: Using 2 mol% of precatalyst C and following the general
procedure, compound 13e was isolated as a white solid
(42.2 mg, 98.0 μmol, 98%) after column chromatography (SiO2,
hexane/EtOAc, 30:1, Rf = 0.14). 1H-NMR (400 MHz, CDCl3):
δ = 8.75 – 8.68 (m, 2H), 8.15 (d, J = 8.2 Hz, 1H), 7.91 (dd, J =
7.5, 1.7 Hz, 1H), 7.80 (s, 1H), 7.68 – 7.56 (m, 2H), 7.52 – 7.47
(m, 1H), 7.37 – 7.30 (m, 2H), 7.29 – 7.25 (m, 2H), 7.19 (td, J =
7.3, 1.4 Hz, 1H), 7.02 (s, 1H), 6.58 (d, J = 2.5 Hz, 1H), 6.08 (d, J
= 2.4 Hz, 1H), 3.82 (s, 3H), 2.90 (s, 3H) ppm. 13C{1H}-NMR
(101 MHz, CDCl3): δ = 162.0, 161.5, 159.0, 158.4, 141.7, 139.1,
132.1, 131.3, 131.2, 130.7, 130.4, 129.9, 129.4, 129.4, 128.7,
126.8, 126.6, 126.3, 126.2, 126.1, 125.5, 125.2, 122.8, 122.6,
+
HR-MS (ESI): calculated m/z for C22H17O4 ([M+H]+): 345.1121;
found 345.1120. FTIR (ATR, neat): 휈̃ = 3062, 3003, 2955, 2930,
2896, 2835, 2781, 1627, 1605, 1574, 1509, 1478, 1462, 1443,
1360, 1335, 1288, 1242, 1194, 1175, 1125, 1106, 1055, 1036,
985, 926, 907, 874, 853, 828, 809, 795, 782, 773, 749, 728, 680,
664, 649, 635, 624, 614, 564, 532, 512 cm-1.
1,3-di-tert-butyl-11-(4-methoxyphenyl)dibenzo[b,f]oxepine
13i: Using 2 mol% of precatalyst C and following the general
procedure, compound 13i was isolated as a white solid (27.0 mg,
65.4 μmol, 65%) after column chromatography (SiO2,
hexane/EtOAc, 50:1, Rf = 0.26 (hexane/EtOAc, 30:1)). Mp: 205-
207 °C. 1H-NMR (400 MHz, CDCl3): δ = 7.32 – 7.26 (m, 2H),
7.24 – 7.08 (m, 6H), 7.00 (s, 1H), 6.86 – 6.81 (m, 2H), 3.80 (s,
3H), 1.34 (s, 9H), 1.01 (s, 9H) ppm. 13C{1H}-NMR (101 MHz,
CDCl3): δ = 164.8, 160.5, 159.1, 151.5, 150.9, 145.1, 137.9,
132.3, 128.64, 128.63, 128.5, 126.3, 126.1, 124.8, 122.9, 120.8,
114.6, 113.7, 55.4, 37.2, 34.8, 32.2, 31.4 ppm. HR-MS (ESI):
120.9, 115.4, 98.7, 97.0, 55.7, 55.6 ppm.
HR-MS (ESI):
calculated m/z for C30H23O3 ([M+H]+): 431.1642; found
431.1641. FTIR (ATR, neat): 휈̃ = 3067, 3004, 2933, 2838, 1607,
1567, 1483, 1450, 1434, 1415, 1328, 1214, 1196, 1141, 1109,
1089, 1065, 1044, 982, 939, 884, 850, 838, 758, 740, 724, 673,
627, 570, 517 cm-1.
+
1,3-dimethoxy-11-(pyren-1-yl)dibenzo[b,f]oxepine 13f: Using
2 mol% of precatalyst C and following the general procedure,
compound 13f was isolated as a yellow solid (44.4 mg,
97.6 μmol, 98%) after column chromatography (SiO2,
hexane/EtOAc, 50:1, Rf = 0.08). 1H-NMR (400 MHz, CDCl3):
δ = 8.32 (d, J = 9.2 Hz, 1H), 8.19 – 8.14 (m, 2H), 8.14 – 8.02 (m,
4H), 8.01 – 7.94 (m, 2H), 7.38 (dd, J = 7.5, 1.6 Hz, 1H), 7.34
(ddd, J = 8.8, 7.1, 1.7 Hz, 1H), 7.29 (dd, J = 8.1, 1.5 Hz, 1H),
7.21 (td, J = 7.3, 1.5 Hz, 1H), 7.01 (s, 1H), 6.61 (d, J = 2.4 Hz,
1H), 6.07 (d, J = 2.5 Hz, 1H), 3.83 (s, 3H), 2.81 (s, 3H) ppm.
13C{1H}-NMR (101 MHz, CDCl3): δ = 162.1, 161.6, 159.0, 158.4,
140.9, 139.7, 131.7, 131.6, 131.3, 131.2, 130.2, 129.5, 129.4,
128.2, 127.7, 126.9, 126.7, 125.9, 125.6, 125.23, 125.16, 124.9,
124.8, 124.7, 124.5, 121.0, 115.7, 98.6, 97.0, 55.63, 55.58 ppm.
+
calculated m/z for C29H33O2 ([M+H]+): 413.2475; found
413.2476. FTIR (ATR, neat): 휈̃ = 3068, 2954, 2903, 2866, 2835,
1604, 1575, 1542, 1509, 1480, 1444, 1396, 1362, 1285, 1246,
1223, 1192, 1176, 1150, 1105, 1032, 973, 906, 869, 851, 826,
772, 753, 729, 680, 646, 590, 577, 563, 533 cm-1.
11-(4-methoxyphenyl)-4-phenyldibenzo[b,f]oxepine
13j:
Using 2 mol% of precatalysts C and following the general
procedure, compound 13j was isolated as a white solid (37.0 mg,
98.3 μmol, 98%) after column chromatography (SiO2,
hexane/EtOAc, 30:1, Rf = 0.20). 1H-NMR (400 MHz, CDCl3):
δ = 7.70 – 7.65 (m, 2H), 7.56 – 7.49 (m, 2H), 7.49 – 7.42 (m, 3H),
7.38 (dd, J = 7.4, 1.8 Hz, 1H), 7.23 (dd, J = 7.1, 2.2 Hz, 1H),
7.09 (t, J = 7.7 Hz, 1H), 7.06 – 6.89 (m, 6H), 6.25 (dd, J = 7.4,
1.9 Hz, 1H), 3.88 (s, 3H) ppm. 13C{1H}-NMR (101 MHz, CDCl3):
δ = 159.5, 157.7, 155.0, 142.1, 138.3, 135.5, 135.3, 133.0, 131.3,
131.2, 130.4, 130.3, 129.9, 129.2, 129.1, 128.1, 127.5, 127.1,
124.8, 124.4, 121.1, 113.9, 55.5 ppm. HR-MS (ESI): calculated
+
HR-MS (ESI): calculated m/z for C32H23O3 ([M+H]+): 455.1642;
found 455.1641. FTIR (ATR, neat): 휈̃ = 3038, 3006, 2934, 2836,
1605, 1567, 1484, 1454, 1435, 1415, 1327, 1289, 1245, 1213,
1196, 1153, 1141, 1087, 1045, 938, 905, 843, 752, 681, 634,
546, 506 cm-1.
+
m/z for C27H21O2 ([M+H]+): 377.1536; found 377.1535. FTIR
(ATR, neat): 휈̃ = 3032, 3000, 2954, 2930, 2906, 2834, 1603,
1573, 1506, 1483, 1446, 1425, 1362, 1285, 1241, 1198, 1174,
11-([1,1':3',1''-terphenyl]-5'-yl)-1,3-dimethoxydibenzo[b,f]
oxepine 13g: Using 2 mol% of precatalyst C and following the
general procedure, compound 13g was isolated as a white solid
8
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