Full Paper
14.4. IR (neat): νmax = 3020, 2972, 1739, 1659, 1540, 1450, 1371,
6.80 (m, 1 H), 6.02 (d, J = 10.4 Hz, 1 H), 4.24 (m, 1 H), 3.58 (s, 3 H),
˜
1291, 1216, 1123, 1021 cm–1. HRMS (ESI+) m/z [M + H]+ calcd. for 2.82 (dd, J = 16.8, 4.4 Hz, 1 H), 2.67 (dd, J = 16.8, 3.3 Hz, 1 H) ppm.
C21H21N2O2 333.1603, found 333.1601.
13C NMR (75 MHz, CDCl3): δ = 197.2, 165.0, 159.3, 144.6, 140.0, 136.8,
130.5, 129.9, 129.5, 127.9, 127.7, 126.4, 121.6, 117.7, 116.4, 113.8,
(3aR,7aR)-1-(2,4-Dimethylphenyl)-3a-hydroxy-2-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3e, Athropisomers
Mixture): Purification by washing with heptane afforded the pale
yellow solid product 3e (mixture of atropisomers). Yellow solid
(249 mg, 75 %), m.p. 118 °C. 1H: δ = NMR (500 MHz, CDCl3)δ = 7.40–
7.10 (m, 7 H), 6.93 (m, 3 H), 6.00 (m, 1 H), 4.37–4.26 (m, 1 H), 2.78–
90.9, 70.2, 55.4, 36.7 ppm. IR (neat): νmax = 3054, 2962, 1741, 1683,
˜
1570, 1492, 1395, 1288, 1254, 1182, 1145, 1116, 1044 cm–1. HRMS
(ESI+) m/z [M + H]+ calcd. for C20H19N2O3 335.1396, found 335.1389.
(3aR,7aR)-2-(4-Bromophenyl)-1-(4-chlorophenyl)-3a-hydroxy-
7,7a-dihydro-1H-benzo[d]imidazol-6(3aH)-one (3j): Purification
2.70 (m, 1 H), 2.60–2.47 (m, 1 H), 2.25–2.21 (s, 3 H), 2.04–1.85 (s, 3 by washing with heptane afforded the pale yellow solid product 3j.
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 197.5/197.0, 165.0/164.7, Pale yellow solid (309 mg, 74 %), m.p. 123 °C. 1H NMR (300 MHz,
145.3/144.7, 138.5/137.8, 136.7/135.7, 135.3/134.4, 132.7/132.3,
130.9/130.8, 130.8/130.7, 129.7/129.6, 128.7/128.5, 128.3/128.2,
[D6]DMSO): δ = 7.53–7.49 (m, 2 H), 7.42–7.37 (m, 2 H), 7.26–7.21 (m,
2 H), 6.98–6.92 (m, 2 H), 6.67 (dd, J = 10.2, 1.4 Hz, 1 H), 5.95 (d, J =
128.0/126.5, 125.9/125.6, 91.0/90.3, 70.7/67.7, 36.7/35.3, 21.1/21.1, 10.2 Hz, 1 H), 4.16 (m, 1 H), 2.88 (dd, J = 6.8, 4.4 Hz, 1 H), 2.46 (dd,
17.7/17.7. IR (neat): νmax = 3013, 2969, 1739, 1688, 1553, 1496, 1395, J = 6.8, 3.4 Hz, 1 H) ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 196.4,
˜
1293, 1247, 1119, 1029 cm–1. HRMS (ESI+) m/z [M + H]+ calcd. for 161.3, 144.6, 139.2, 131.3, 131.2, 130.9, 130.6, 129.6, 129.2, 128.4,
C
21H21N2O2 333.1603, found 333.1602.
125.7, 123.9, 115.6, 91.0, 69.3, 36.4 ppm. IR (neat): νmax = 3044,
˜
2944, 1748, 1652, 1622, 1598, 1548, 1487, 1278, 1157, 1128,
1089, 1068, 1009 cm–1. HRMS (ESI+) m/z [M + H]+ calcd. for
C19H15BrClN2O2 417.0005, found 417.0013.
(3aR,7aR)-1-(2,5-Dimethylphenyl)-3a-hydroxy-2-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3f, Athropisomers Mix-
ture): Purification by washing with heptane afforded the pale yel-
low solid product 3f (mixture of two atropisomers). Yellow solid
(243 mg, 73 %), m.p. 120 °C. 1H: δ = NMR (500 MHz, CDCl3)δ = 7.40–
7.24 (m, 3 H), 7.21–7.16 (m, 2 H), 7.01–6.78 (m, 1 H), 6.01 (m, 1 H),
(3aR,7aR)-1-(4-Chlorophenyl)-3a-hydroxy-2-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3k): Purification by
washing with heptane afforded the brown solid product 3k. Yellow
4.42–4.27 (m, 1 H), 2.80–2.71 (m, 1 H), 2.60–2.49 (m, 1 H), 2.26–2.25 solid (261 mg, 77 %), m.p. 124 °C. 1H NMR (300 MHz, [D6]DMSO):
(s, 3 H), 2.03–1.82 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 197.6/
δ = 7.40–7.28 (m, 7 H), 6.96–6.92 (m, 2 H), 6.85 (s, 1 H), 6.68 (dd,
197.1, 165.3/164.8, 145.2/144.6, 137.8/137.4, 137.3/136.9, 136.8, J = 10.2, 1.3 Hz, 1 H), 5.95 (d, J = 10.2 Hz, 1 H), 4.15 (m, 1 H), 2.88
131.9, 131.6/131.5, 131.0, 129.7, 129.1/128.8, 128.7/128.4, 127.0, (dd, J = 16.8, 4.3 Hz, 1 H), 2.47 (d, J = 16.8 Hz, 1 H) ppm. 13C NMR
126.2/126.0, 91.1/90.4, 70.7/67.9, 36.9/35.4, 21.0, 17.5/17.4. IR (neat): (75 MHz, [D6]DMSO): δ = 196.5, 162.3, 144.8, 139.6, 130.8, 130.3,
νmax = 3068, 2918, 1737, 1674, 1547, 1496, 1375, 1295, 1276, 1193,
130.0, 129.5, 128.6, 128.4, 128.2, 128.0, 125.6, 115.6, 91.0, 69.3, 36.4
ppm. HRMS (ESI+) m/z [M + H]+ calcd. for C19H16ClN2O2 339.0900,
found 339.0878.
˜
1157, 1124, 1038 cm–1. HRMS (ESI+) m/z [M + H]+ calcd. for
C21H21N2O2 333.1603, found 333.1602.
(3aR,7aR)-3a-Hydroxy-1-(4-methoxyphenyl)-2-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3g): Purification by
washing with heptane afforded the pale yellow solid product 3g.
Yellow solid (268 mg, 80 %), m.p. 131 °C. 1H: δ = NMR (300 MHz,
CDCl3)δ = 7.36–7.33 (m, 2 H), 7.29–7.17 (m, 3 H), 6.92–6.86 (m, 3 H),
6.79–6.76 (m, 2 H), 6.00 (d, J = 10.4 Hz, 1 H), 4.16 (m, 1 H), 3.74 (s,
3 H), 2.82 (dd, J = 7.0 Hz, 4.4 Hz, 1 H), 2.66 (dd, J = 7.0, 2.5 Hz, 1 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 197.4, 165.4, 158.9, 144.5, 132.7,
130.8, 129.6, 129.3, 129.1, 128.4, 126.3, 116.4, 115.1, 90.8, 70.6, 55.6,
(3aR,7aR)-3a-Hydroxy-2-phenyl-1-(p-tolyl)-7,7a-dihydro-1H-
benzo[d]imidazol-6(3aH)-one (3l): Purification by washing with
heptane afforded the white solid product 3l. White solid (256 mg,
80 %), m.p. 121 °C. 1H NMR (300 MHz, [D6]DMSO): δ = 7.35–7.21 (m,
5 H), 7.13 (d, J = 8.2 Hz, 2 H), 6.84–6.79 (m, 3 H), 6.65 (d, J = 10.2 Hz,
1 H), 5.94 (d, J = 10.2 Hz, 1 H), 4.02 (m, 1 H), 2.83 (dd, J = 16.7,
4.3 Hz, 1 H), 2.44 (dd, J = 16.7, 2.9 Hz, 1 H), 2.24 (s, 3 H) ppm. 13C
NMR (75 MHz, [D6]DMSO): δ = 196.7, 162.9, 144.7, 138.3, 136.2,
130.4, 130.1, 128.5, 128.0, 127.0, 125.4, 90.8, 70.0, 36.3, 20.5 ppm. IR
36.7 ppm. IR (neat): νmax = 3064, 2877, 1741, 1688, 1588, 1550, 1509,
(neat): νmax = 3024, 2981, 1741, 1688, 1590, 1559, 1511, 1494, 1445,
˜
˜
1494, 1445, 1375, 1291, 1274, 1249, 1181, 1157, 1128, 1104, 1036 1370, 1356, 1271, 1181, 1152, 1124, 1050, 1027 cm–1. HRMS (ESI+)
cm–1. HRMS (ESI+) m/z [M + H]+ calcd. for C20H19N2O3 335.1396, m/z [M + H]+ calcd. for C20H19N2O2 319.1447, found 319.1445.
found 335.1394.
(3aR,7aR)-3a-hydroxy-2-methyl-1-phenyl-7,7a-dihydro-1H-
(3aR,7aR)-2-(4-Bromophenyl)-3a-hydroxy-1-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3h): Purification by
washing with heptane afforded the pale yellow solid product 3h.
benzo[d]imidazol-6(3aH)-one (3m): Purification by washing with
heptane afforded the grey solid product 3m. Brown solid (180 mg,
1
73 %), m.p. 103 °C. H NMR (300 MHz, CDCl3): δ = 7.43–7.27 (m, 4
Yellow solid (311 mg, 81 %), m.p. 132 °C. 1H NMR (300 MHz, H), 7.08–7.04 (m, 2 H), 6.76 (dd, J = 10.3, 1.4 Hz, 1 H), 5.98 (d, J =
[D6]DMSO): δ = 7.47 (m, 2 H), 7.37–7.20 (m, 5 H), 6.95 (m, 2 H), 6.85
(s, 1 H), 6.67 (d, J = 10.2 Hz, 1 H), 5.96 (d, J = 10.2 Hz, 1 H), 4.12 (m,
1 H), 2.86 (dd, J = 6.8, 4.4 Hz, 1 H), 2.46 (dd, J = 6.8, 3.2 Hz, 1 H)
ppm. 13C NMR (75 MHz, [D6]DMSO): δ = 196.5, 161.7, 144.6, 140.4,
10.3 Hz, 1 H), 4.31 (m, 1 H), 2.75 (dd, J = 16.8, 4.6 Hz, 1 H), 2.51 (dd,
J = 16.8, 2.7 Hz, 1 H), 1.83 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 196.8, 164.2, 144.7, 137.9, 130.1, 128.1, 127.0, 126.0, 90.3, 68.2,
53.6, 36.1, 15.5 ppm. HRMS (ESI+) m/z [M + H]+ calcd. for C14H15N2O2
131.1, 130.6, 129.6, 129.5, 126.9, 126.9, 125.6, 123.8, 90.9, 69.7, 36.3 243.1134, found 243.1131. IR (neat): νmax = 3051, 2989, 1736, 1690,
˜
ppm. IR (neat): νmax = 3054, 2979, 1737, 1685, 1594, 1543, 1487,
1579, 1492, 1405, 1295, 1184, 1148, 1121, 1077, 1036 cm–1
.
˜
1400, 1290, 1274, 1182, 1155, 1124, 1033 cm–1. HRMS (ESI+) m/z [M
(3aR,7aR)-1-(4-Chlorophenyl)-3a-hydroxy-2-methyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3n): Purification by
washing with heptane afforded the grey solid product 3n. Grey
solid (205 mg, 74 %), m.p. 116 °C. 1H NMR (300 MHz, CDCl3): δ =
7.40–7.37 (m, 2 H), 7.00 (m, 2 H), 6.75 (dd, J = 10.2, 1.4 Hz, 1 H),
+ H]+ calcd. for C19H16BrN2O2 383.0395, found 383.0393.
(3aR,7aR)-3a-Hydroxy-2-(3-methoxyphenyl)-1-phenyl-7,7a-di-
hydro-1H-benzo[d]imidazol-6(3aH)-one (3i): Purification by
washing with heptane afforded the pale yellow solid product 3i.
Yellow solid (271 mg, 81 %), m.p. 116 °C. 1H NMR (300 MHz, CDCl3): 5.98 (d, J = 10.2 Hz, 1 H), 4.27 (m, 1 H), 2.76 (dd, J = 17.0, 4.5 Hz, 1
δ = 7.31–7.21 (m, 3 H), 7.11–7.05 (m, 1 H), 6.97–6.88 (m, 5 H), 6.84– H), 2.48 (dd, J = 17.0, 2.4 Hz, 1 H), 1.83 (s, 3 H) ppm. 13C NMR
Eur. J. Org. Chem. 0000, 0–0
5
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim