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Organic & Biomolecular Chemistry
DOI: 10.1039/C7OB02259J
ARTICLE
Journal Name
7
.24 (m, 2 H, Ar), 7.19 – 7.07 (m, 2 H, Ar), 5.75 (s, 0.12 H, H- 140.7, 137.8, 137.6, 136.9, 128.8, 128.7 (2C), 128.6, 128.5,
1
3
1
min), 5.66 (s, 0.88 H, H-4maj); C{ H} NMR (101 MHz, Pyridine- 128.0, 127.7, 127.2 (2C), 127.0, 126.9 (2C), 126.6, 126.0, 125.9,
4
d
1
1
1
5
) δ 184.6, 150.2, 150.1, 146.5, 139.3, 138.1, 137.8, 135.1, 125.8, 125.6, 125.4, 122.8 (2C), 114.2, 113.9, 113.7, 98.0 (C-
1
9
32.4, 131.5, 130.0, 129.7, 129.5, 129.4, 129.1, 128.9, 128.8,
5
min), 95.3 (C-5maj), 65.8 (C-4min), 64.9 (C-4maj); F NMR (376
) δ -116.25 – -116.31 (m, 0.14 F, Armin), -
12.4, 110.0, 96.8 (C-5min), 96.6 (C-5maj), 73.4 (C-4min), 72.3 (C- 116.41 – -116.47 (m, 0.86 F, Armaj); HRMS (ESI) m/z calcd. for
28.7 (2C), 128.6, 128.4, 127.5, 127.2, 125.9, 120.4, 119.2, MHz, Pyridine-d
5
+
+
4maj); HRMS (ESI) m/z calcd. for C22
H
18
N
3
OS [M+H] 372.1165,
21 2
C H18FN OS [M+H] 365.1118, found 365.1102; IR (neat)
-
1
-1
found 372.1150; IR (neat)
ꢀmax/cm 3317, 3197, 2243, 1596,
ꢀmax/cm 3158, 2809, 1618, 1587, 1552, 1489, 1451, 1407,
585, 1495, 1452, 1395, 1350, 1231, 1204, 1173, 1131, 1102, 1356, 1307, 1239, 1220, 1132, 1082, 1020, 998, 970, 951, 901,
1
1089, 1049, 990, 892, 852, 820, 748, 699.
834, 825, 817, 786, 740, 696.
(
±
)-5-Hydroxy-5-isopropyl-1,4-diphenylimidazolidine-2-thione
(±)-5-Hydroxy-1,5-diphenyl-4-(m-tolyl)imidazolidine-2-thione
5aag). Column chromatography on silica gel with (5faa). Column chromatography on silica gel with
(
cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5aag as white cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5faa as white
1
amorphous solid contaminated by uncharacterized by- amorphous solid (230 mg, 64%, d.r. 85/15). H NMR (400 MHz,
1
products (153 mg, 49%, d.r. 69/31). H NMR (400 MHz, Pyridine-d
5
) δ 11.19 (s, 0.85 H, NHmaj), 11.09 (s, 0.15 H, NHmin),
5
Pyridine-d , selected data) δ 11.24 (s, 0.31 H, NHmin), 10.78 (s, 10.19 (s, br, 0.15 H, OHmin), 9.46 (s, 0.85 H, OHmaj), 8.06 – 8.02
0.69 H, NHmaj), 10.24 (s, 0.31 H, OHmin), 9.51 (s, 0.69 H, OHmaj), (m, 0.30 H, Armin), 8.01 – 7.96 (m, 1.70 H, Armaj), 7.93 – 7.87 (m,
7.97 – 7.95 (m, 1.28 H, Armaj), 7.91 – 7.87 (m, 0.69 H, Armaj), 1.70 H, Armaj), 7.68 – 7.63 (m, 0.30 H, Armin), 7.39 – 7.33 (m, 2
7.78 – 7.74 (m, 1.28 H, Armaj), 7.44 – 7.40 (m, 1.69 H, Ar), 7.37 H, Ar), 7.32 – 7.23 (m, 2 H, Ar), 7.19 – 6.96 (m, 5.85, Ar), 8.06 –
– 7.31 (m, 3.94 H, Ar), 7.08 – 7.03 (m, 1 H, Ar), 5.68 (s, 0.31 H, 8.02 (m, 0.30 H, Armin), 6.95 – 6.90 (m, 0.15, Armin), 5.75 (s, 0.15
H-4min), 5.40 (s, 0.69 H, H-4maj), 2.30 (ep, J = 6.9 Hz, 1 H, CHipr), H, H-4min), 5.67 (s, 0.85 H, H-4maj), 2.23 (s, 0.45 H, CH3min), 2.08
1
3
1
.23 (d, J = 6.9 Hz, 3 H, CH3ipr), 1.21 (d, J = 6.9 Hz, 3 H, CH3ipr); (s, 2.55 H, CH3maj); C{ H} NMR (101 MHz, Pyridine-d
1
5
) δ 184.1
1
3
1
C{ H} NMR (101 MHz, Pyridine-d
5
) δ 181.8, 137.3, 137.1, (C-2min), 184.1 (C-2maj), 141.5, 139.2, 138.9, 138.8, 137.6,
1
1
6
ꢀ
1
34.0, 129.9, 128.4, 128.2, 128.0, 127.6, 127.2, 126.9, 126.7, 137.3, 135.6, 129.8, 129.6, 129.4, 129.3, 129.2 (2C), 129.1,
26.6, 126.2, 125.4, 97.5 (C-5maj), 95.7 (C-5min), 71.0 (C-4min), 129.0, 128.9, 128.8, 128.4, 128.2, 127.9, 127.8, 127.5, 127.3,
1.6 (C-4maj), 34.7 (CHipr), 16.1 (CH3ipr), 15.2 (CH3ipr); IR (neat) 126.8, 126.6 (2C), 125.5, 125.3, 125.2, 124.5, 123.9, 123.8,
-1
max/cm 3156, 2968, 1699, 1596, 1494, 1450, 1409, 1304, 123.6, 123.3, 123.1, 122.8, 99.6 (C-5min), 96.9 (C-5maj), 73.1 (C-
230, 1131, 1026, 968, 825, 752. min), 72.1 (C-4maj), 21.0 (C-CH3min), 20.9 (C-CH3maj); HRMS (ESI)
)-4,5-Bis(4-chlorophenyl)-5-hydroxy-1-phenylimidazolidine- m/z calcd. for C22
4
+
(±
H
21
N
2
OS [M+H] 361.1369, found 361.1342;
-
1
2-thione (5bab). Column chromatography on silica gel with IR (neat) ꢀmax/cm 3177, 3035, 1596, 1548, 1538, 1492, 1426,
cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5bab as white 1348, 1305, 1241, 1197, 1140, 1041, 1022, 969, 875, 823, 798,
1
amorphous solid (230 mg, 56%, d.r. 93/7). H NMR (400 MHz, 753, 715, 698.
Pyridine-d
5
) δ 11.29 (s, 0.93 H, NHmaj), 11.18 (s, 0.07 H, NHmin),
(±)-4-(3-Bromophenyl)-5-hydroxy-1,5-diphenylimidazolidine-
0.41 (s, 0.07 H, OHmin), 9.74 (s, 0.93 H, OHmaj), 8.01 – 7.99 (m, 2-thione (5eaa). Column chromatography on silica gel with
1
0
1
.14 H, Armin), 7.95 – 7.90 (m, 1.86 H, Armaj), 7.86 – 7.80 (m, cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5eaa as white
1
.86 H, Armaj), 7.57 – 7.52 (m, 0.14 H, Armin), 7.45 – 7.41 (m, 2 amorphous solid (326 mg, 77%, d.r. 90/10). H NMR (400 MHz,
H, Ar), 7.40 – 7.36 (m, 1H, Ar), 7.36 – 7.12 (m, 5H, Ar), 7.14 – Pyridine-d
5
) δ 11.21 (s, 0.90 H, NHmaj), 11.11 (s, 0.10 H, NHmin),
7
.03 (m, 1H), 5.73 (s, 0.07 H, H-4min), 5.63 (s, 0.93 H, H-4maj); 9.69 (s, br, 1 H, OH), 8.02 – 7. 92 (m, 2 H, Ar), 7.91 – 7.86 (m, 2
1
3
1
C{ H} NMR (101 MHz, Pyridine-d
32.9, 132.8, 132.7, 128.5, 128.4, 128.3, 127.3, 127.2, 127.1, 7.33 (m, 1H, Ar), 7.29 – 7.22 (m, 1 H, Ar), 7.20 – 7.10 (m, 4 H,
25.7, 95.1, 70.3; HRMS (ESI) m/z calcd. for C21 OS Ar), 7.09 – 7.02 (m, 2 H, Ar), 5.75 (s, 0.10 H, H-4min), 5.68 (s,
5
) δ 183.2, 138.6, 137.8, H, Ar) 7.83 – 7.79 (m, 1 H, Ar), 7.54 – 7.46 (m, 1H, Ar), 7.39 –
1
1
H
2 2
16Cl N
+
-1
13
1
[M+H] 414.0360, found 414.0378; IR (neat)
ꢀ
max/cm 3156, 0.90 H, H-4maj); C{ H} NMR (101 MHz, Pyridine-d
5
) δ 183.0,
2
1
7
948, 1594, 1553, 1499, 1454, 1385, 1348, 1308, 1285, 1228, 139.8, 137.9, 136.8, 130.0, 129.8, 128.8, 128.4, 127.2, 127.0
207, 1176, 1127, 1089, 1038, 1015, 998, 971, 897, 825, 801, (2C), 126.6, 125.8, 125.6, 121.1, 95.6, 70.4; HRMS (ESI) m/z
+
OS [M+H] 425.0318, found 425.0336; IR
48, 695.
calcd. for C21
H
18BrN
2
-1
(± (neat) ꢀmax/cm 3145, 2785, 1595, 1596, 1549, 1538, 1496,
-thione (5daa). Column chromatography on silica gel with 1475, 1427, 1409, 1344, 1305, 1268, 1236, 1201, 1134, 1040,
)-4-(2-Fluorophenyl)-5-hydroxy-1,5-diphenylimidazolidine-
2
cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5daa as white 996, 948, 849, 826, 773, 761, 733, 697.
1
amorphous solid (189 mg, 52%, d.r. 86/14). H NMR (400 MHz,
Pyridine-d ) δ 11.15 (s, 0.86 H, NHmaj), 11.12 (s, 0.14 H, NHmin), 2-thione (5baa). Column chromatography on silica gel with
0.46 (s, br, 0.14 H, OHmin), 9.53 (s, 0.86 H, OHmaj), 8.11 – 8.07 cyclohexane/EtOAc/TEA = 7:3:0.5 afforded 5baa as white
(±)-4-(4-Chlorophenyl)-5-hydroxy-1,5-diphenylimidazolidine-
5
1
1
(
m, 0.28 H, Armin), 8.03 – 7.98 (m, 0.86 H, Armaj), 7.97 – 7.94 (m, amorphous solid (201 mg, 53%, d.r. 88/12). H NMR (400 MHz,
.86 H, Ar), 7.93 – 7.87 (m, 1.72, Armaj), 7.72 – 7.67 (m, 0.28 H, Pyridine-d ) δ 11.22 (s, 0.88 H, NHmaj), 11.18 (s, 0.12 H, NHmin),
Armin), 7.39 – 7.31 (m, 1.86 H, Ar), 7.30 – 7.24 (m, 1.86 H, Ar), 10.41 (s, br, 0.12 H, OHmin), 9.55 (s, 0.88 H, OHmaj), 8.04 – 7.98
1
5
7
.20 – 7.15 (m, 1.86 H, Ar), 7.14 – 6.98 (m, 3.42 H, Ar), 6.10 (s, (m, 0.24 H, Armin) 7.97 – 7.92 (m, 1.76 H, Armaj), 7.90 – 7.81 (m,
1
3
1
0.14 H, H-4min), 6.05 (s, 0.86 H, H-4maj); C{ H} NMR (101 MHz, 2 H, Ar), 7.41 – 7.31 (m, 5 H, Ar), 7.30 – 7.17 (m, 3.76 H, Ar),
) δ 183.1 (C-2min), 182.8 (C-2maj), 161.3, 158.8, 7.13 – 6.98 (m, 1.24 H, Ar), 5.74 (s, 0.12 H, H-4min), 5.65 (s, 0.88
Pyridine-d
5
1
0 | J. Name., 2012, 00, 1-3
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