13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 21.72 (C-3), 23.08 (C-8), 25.91 (C-4), 27.58 (C-9), 32.51 (C-7), 34.65
3
(C-2), 35.15 (C-6ꢁ), 38.42 (C-6), 40.69 (C-5), 46.47 (C-1), 62.37 (C-10), 125.38 (C-5ꢁ), 129.00 (C-4ꢁ), 142.51 (C-2ꢁ).
C H N O S.
14 22
2 2
1-Methyl-2-{[(1R,2R,5R)-6,6-dimethylbicyclo[3.1.1]heptyl-2]methylsulfonyl}-1H-imidazole (7). Light-yellow
20
–1
powder, mp 68–69°C, [ꢂ] +3.82° (c 0.61, EtOH). IR spectrum (ꢃ, cm ): 1324 [ꢃ (SO )], 1122 [ꢃ (SO )].
D
as
2
s
2
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.88 (3H, s, Me-8), 1.23 (3H, s, Me-9), 1.37 (1H, d, J = 10.3, H-7ꢅ),
3
1.43–1.57 (1H, m, H-3ꢂ), 1.75–1.98 (5H, m, H-1, H-5, H-3ꢅ, H-4ꢂ, H-4ꢅ), 2.12 (1H, ddd, J = 10.6, 5.7, 5.5, H-7ꢂ), 2.76 (1H,
quin, J = 7.4, H-2), 3.38–3.50 (2H, m, H-10ꢂ, H-10ꢅ), 4.01 (3H, s, Me-6ꢁ), 7.00 (1H, s, H-5ꢁ), 7.15 (1H, s, H-4ꢁ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 20.07 (C-8), 21.83 (C-3), 23.25 (C-7), 24.23 (C-4), 26.62 (C-9), 30.25
3
(C-2), 35.13 (C-6ꢁ), 39.57 (C-6), 40.26 (C-5), 45.62 (C-1), 61.15 (C-10), 125.29 (C-5ꢁ), 129.00 (C-4ꢁ), 142.80 (C-2ꢁ).
C H N O S.
14 22
2 2
1-Methyl-2-{[(1R,3S,4R,6S)-4,7,7-trimethylbicyclo[4.1.0]heptyl]sulfonyl}-1H-imidazole (8). Light-beige powder,
20
–1
mp 97–98°C, [ꢂ] –5.59° (c 0.59, EtOH). IR spectrum (ꢃ, cm ): 1308 [ꢃ (SO )], 1126 [ꢃ (SO )].
D
as
2
s
2
PMR spectrum (300 MHz, CDCl , ꢄ, ppm, J/Hz): 0.59 (1H, td, J = 8.7, 7.4, H-1), 0.74 (1H, q, J = 8.5, H-6), 0.98–1.08
3
(1H, m, H-5ꢂ), 1.01 (3H, s, Me-8), 1.03 (3H, s, Me-9), 1.20 (3H, d, J = 7.0, Me-10), 1.23–1.34 (1H, m, H-2ꢂ), 1.99 (1H, ddd,
J = 13.9, 8.5, 3.7, H-2ꢅ), 2.13 (1H, dt, J = 15.3, 8.2, H-5ꢅ), 2.48 (1H, sept, J = 7.4, H-4), 3.74 (1H, ddd, J = 12.0, 7.4, 3.7,
H-3), 4.01 (3H, s, Me-6ꢁ), 7.00 (1H, s, H-4ꢁ), 7.17 (1H, s, H-5ꢁ).
13
C NMR spectrum (75 MHz, CDCl , ꢄ, ppm): 15.18 (C-9), 17.31 (C-2), 17.65 (C-10), 18.38 (C-7), 19.56 (C-6),
3
21.67 (C-1), 26.36 (C-4), 26.88 (C-5), 28.14 (C-8), 35.32 (C-6ꢁ), 62.70 (C-3), 125.22 (C-5ꢁ), 129.11 (C-4ꢁ), 142.35 (C-2ꢁ).
C H N O S.
14 22
2 2
2-{[(1S,2S,5R)-2-Isopropyl-5-methylcyclohexyl]sulfonyl}-1H-benzimidazole (9). Pale-yellow powder, mp 223–
20
20
–1
224°C, [ꢂ] 0° (c 0.14, EtOH), [ꢂ] –33.57° (c 0.14, CHCl ). IR spectrum (ꢃ, cm ): 1332 [ꢃ (SO )], 1134 [ꢃ (SO )].
D
D
3
as
2
s
2
PMR spectrum (300 MHz, CDCl + DMSO-d , ꢄ, ppm, J/Hz): 0.71 (3H, d, J = 6.5, Me-7), 0.74–0.93 (1H, m, H-4ax),
3
6
0.78 (3H, d, J = 6.5, Me-10), 0.83 (3H, d, J = 6.7, Me-9), 1.10 (1H, ddd, J = 14.4, 12.9, 4.7, H-6ax), 1.26–1.36 (1H, m, H-2),
1.78–2.01 (4H, m, H-3ax, H-3eq, H-4eq, H-6eq), 2.05–2.19 (2H, m, H-8, H-5), 4.16–4.22 (1H, m, H-1), 7.36–7.42 (2H, m,
H-5ꢁ, 6ꢁ), 7.69–7.74 (2H, m, H-4ꢁ, 7ꢁ), 13.86 (1H, br.s, NH).
13
C NMR spectrum (75 MHz, CDCl + DMSO-d , ꢄ, ppm): 21.66 (C-9), 21.66 (C-10), 22.16 (C-7), 25.03 (C-3),
3
6
26.48 (C-5), 29.42 (C-8), 35.03 (C-4), 35.96 (C-6), 49.27 (C-2), 62.09 (C-1), 112.43 (C-4ꢁ), 120.80 (C-7ꢁ), 123.02 (C-5ꢁ),
125.05 (C-6ꢁ), 148.51 (C-2ꢁ). C H N O S.
17 24
2 2
2-{[(1R,2S,5R)-6,6-Dimethylbicyclo[3.1.1]heptyl-2]methylsulfonyl}-1H-benzimidazole (10). Light-beige powder,
20
–1
mp 158–159°C, [ꢂ] –22.79° (c 0.38, EtOH). IR spectrum (ꢃ, cm ): 1322 [ꢃ (SO )], 1144 [ꢃ (SO )].
D
as
2
s
2
PMR spectrum (300 MHz, CDCl + DMSO-d , ꢄ, ppm, J/Hz): 0.98 (1H, d, J = 10.0, H-7ꢅ), 1.01 (3H, s, Me-8), 1.15
3
6
(3H, s, Me-9), 1.65 (1H, ddt, J = 15.6, 10.3, 5.4, H-3ꢂ), 1.76–2.01 (4H, m, H-1, H-5, H-4ꢂ, H-4ꢅ), 2.06–2.19 (1H, m, H-3ꢅ),
2.33 (1H, dtd, J = 9.9, 6.0, 1.8, H-7ꢂ), 2.80–2.91 (1H, m, H-2), 3.68–3.76 (2H, m, H-10ꢂ, H-10ꢅ), 7.42–7.48 (2H, m, H-5ꢁ, 6ꢁ),
7.71–7.84 (2H, m, H-4ꢁ, 7ꢁ), 13.57 (1H, br.s, NH).
13
C NMR spectrum (75 MHz, CDCl + DMSO-d , ꢄ, ppm): 21.63 (C-3), 23.05 (C-8), 25.81 (C-4), 27.47 (C-9), 32.42
3
6
(C-7), 34.65 (C-2), 38.40 (C-6), 40.58 (C-5), 46.46 (C-1), 62.41 (C-10), 112.65 (C-4ꢁ), 121.53 (C-7ꢁ), 124.20 (C-5ꢁ), 126.25
(C-6ꢁ), 133.40 (C-3aꢁ), 142.95 (C-7aꢁ), 148.01 (C-2ꢁ). C H N O S.
17 22
2 2
2-{[(1R,2R,5R)-6,6-Dimethylbicyclo[3.1.1]heptyl-2]methylsulfonyl}-1H-benzimidazole (11). White powder, mp
20
–1
166–167°C, [ꢂ] +2.13° (c 0.39, EtOH). IR spectrum (ꢃ, cm ): 1328 [ꢃ (SO )], 1138 [ꢃ (SO )].
D
as
2
s
2
PMR spectrum (300 MHz, CDCl + DMSO-d , ꢄ, ppm, J/Hz): 0.85 (3H, s, Me-8), 1.19 (3H, s, Me-9), 1.36 (1H, d,
3
6
J = 10.3, H-7ꢅ), 1.51 (1H, dq, J = 13.8, 9.0, H-3ꢂ), 1.76–1.98 (5H, m, H-1, H-5, H-3ꢅ, H-4ꢂ, H-4ꢅ), 2.12 (1H, ddd, J = 10.6,
5.7, 5.5, H-7ꢂ), 2.83 (1H, quin, J = 7.5, H-2), 3.45–3.59 (2H, m, H-10ꢂ, H-10ꢅ), 7.42–7.48 (2H, m, H-5ꢁ, 6ꢁ), 7.73–7.82 (2H,
m, H-4ꢁ, 7ꢁ), 13.13 (1H, br.s, NH).
13
C NMR spectrum (75 MHz, CDCl + DMSO-d , ꢄ, ppm): 20.03 (C-8), 21.77 (C-3), 23.23 (C-7), 24.16 (C-4), 26.54
3
6
(C-9), 30.40 (C-2), 39.61 (C-6), 40.21 (C-5), 45.63 (C-1), 61.17 (C-10), 113.0 (C-4ꢁ), 120.70 (C-7ꢁ), 123.40 (C-5ꢁ), 125.03
(C-6ꢁ), 148.22 (C-2ꢁ). C H N O S.
17 22
2 2
2-{[(1R,3S,4R,6S)-4,7,7-Trimethylbicyclo[4.1.0]heptyl]sulfonyl}-1H-benzimidazole (12). White powder, mp 130–
20
–1
131°C, [ꢂ] +9.25° (c 1.07, EtOH). IR spectrum (ꢃ, cm ): 1306 [ꢃ (SO )], 1140 [ꢃ (SO )].
D
as
2
s
2
PMR spectrum (300 MHz, CDCl + DMSO-d , ꢄ, ppm, J/Hz): 0.61 (1H, td, J = 8.7, 7.4, H-1), 0.72 (1H, q, J = 8.4,
3
6
H-6), 0.93–1.09 (1H, m, H-5ꢂ), 0.99 (3H, s, Me-8), 1.00 (3H, s, Me-9), 1.30 (3H, d, J = 7.0, Me-10), 1.26–1.39 (1H, m, H-2ꢂ),
41