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D. Annibali et al.
bf-CH(O)-), 3.49 (dt, 1H, J 7.2, 8.1 Hz, H-3), 4.39 (dd, 1H, J 6.6, 8.1 Hz, H-2) 6.85 (d, 1H,
J 8.3 Hz, arom H), 6.89 (t, 1H, J 7.3 Hz, arom H), 7.13±7.32 (m, 7H, arom H) ppm; 13C NMR
(CDCl3, ꢁ, 75.4 MHz): 32.17 (-CH2-Bz), 33.99 (-CH2-Ph), 43.85 (C-3), 44.11 (epoxide-CH2-), 50.56
(bf-CH(O)-), 86.56 (C-2), 109.89, 120.67, 124.61, 126.14, 128.28, 128.50, 128.54, 130.46, 141.36,
158.88 (arom C) ppm; IR (KBr): v 3026 2927 (s, C-H), 1595 (m, arom C-H), 1477 (s, aliph C-H),
1230 (s, C-O), 753 (s, arom C-H) cm 1; HRMS (70 eV): 266.131 (Æ5 ppm) (M , 6.4), 235.2 (5.6),
149.0 (13.5), 131.1 (7.9), 91.0 (16.7), 77.0 (12.0), 74.0 (100.0), 57.0 (9.7).
8d (trans): Yield: 0.065 g (42%); colorless oil; 1H NMR (CDCl3, ꢁ, 300 MHz); 1.93±2.12 (m, 2H,
-CH2-Bz), 2.66±2.76 (m, 2H, -CH2-Ph), 2.79 (dd, 1H, J 2.6, 4.9 Hz, epoxide-CHa-), 2.85 (dd, 1H,
J 4.3, 4.9 Hz, epoxide-CHb-), 3.17 (ddd, 1H, J 2.7, 3.9, 5.9 Hz, bf-CH(O-), 3.41 (dt, 1H, J 5.8,
7.1 Hz, H-3), 4.31 (t, 1H, J 5.8 Hz, H-2), 6.83 (d, 1H, J 7.9 Hz, arom H), 6.88 (t, 1H, J 7.5 Hz,
arom H), 7.12±7.32 (m, 7H, arom H) ppm; 13C NMR (CDCl3, ꢁ, 75.4 MHz): 33.05 (-CH2-Ph), 36.72
(-CH2-Bz), 44.21 (C-3), 44.24 (epoxide -CH2-), 53.25 (bf-CH(O)-), 87.99 (C-2), 109.74, 120.72,
124.35, 126.12, 128.26, 128.52, 129.63, 141.18, 159.05 (arom C) ppm; IR (KBr); v 3026 2925 (s,
C-H), 1597 (m, arom C-H), 1479 (s, arom C-H), 1234 (s, C-O), 751 (s, arom C-H) cm 1; HRMS
(70 eV): 266.131 (Æ5 ppm) (M , 3.1), 235.1 (5.7), 149.0 (3.5), 131.1 (3.6), 91.0 (9.3), 77.0 (8.2),
74.0 (100.0), 57.0 (3.3).
1-(3-(2-Phenyl-ethyl)-2,3-dihydro-2-benzofuryl)-2-(1-piperidyl)-ethanol (3a±d; C23H29NO2)
A solution of 0.040 g epoxide 8a (0.15 mmol) in 2 cm3 of distilled piperidine was re¯uxed for 30 h.
The mixture was evaporated to dryness, and the residue was puri®ed via ¯ash chromatography (5 g
silica gel, CH2Cl2/MeOH/NH4OHconc (970/30/1)) to give the amine 3a (cis) (0.038 g, 72%) as a
yellow oil.
1H NMR (CDCl3, ꢁ, 300 MHz): 1.44-1.49 (m, 2H, 1 piperidyl -CH2-), 1.58±1.62 (m, 4H, 2
piperidyl -CH2-), 1.68±1.81 (m, 1H, -CHa-Bz), 2.27±2.54 (m, 4H, -CHb-Bz, 1 piperidyl -N-CH2-,
-CHa-N-), 2.63±2.88 (m, 5H, 1 piperidyl-N-CH2-, -CHb-N-, -CH2-Ph), 3.39 (ddd, 1H, J 4.5, 7.3,
10.5, H-3), 4.02 (dt, 1H, J 3.4, 9.8 Hz, -CH(OH)-), 3.9±4.2 (1H, -OH), 4.35 (dd, 1H, J 7.5,
9.2 Hz, H-2), 6.79 (d, 1H, J 7.9 Hz, arom H), 6.89 (dt, 1H, J 0.9, 7.5 Hz, arom H), 7.11±7.29 (m,
7H, arom H) ppm; 13C NMR (CDCl3, ꢁ, 75.4 MHz): 24.07, 25.94 (3 piperidyl-CH2-), 31.12 (-CH2-
Bz), 33.10 (-CH2-Ph), 43.58 (C-3), 54.62 (2 piperidyl -N-CH2-), 60.42 (-CH2-N-), 67.64 (-CH(OH)-),
89.74 (C-2), 109.31, 120.43, 124.65, 125.81, 128.13, 128.33, 128.45, 130.20, 141.81, 159.30 (arom
C) ppm; IR (KBr): v 3400 (s, O-H), 2935 (s, C-H), 1596 (m, arom C-H) 1476 1459 (s, aliph C-H),
1299 (s, C-O), 753 (s, arom C-H) cm 1; HRMS (70 eV): 351.220 (Æ5 ppm) (M , 2.1), 149.1 (3.5),
128.1 (17.9), 98.1 (100.0), 84.0 (7.9), 91.0 (35.7), 55.0 (22.1).
3b, 3c, and 3d were prepared from 8b (0.091 g, 0.34 mmol), 8c (0.045 g, 0.17 mmol), and 8d
(0.040 g, 0.15 mmol), respectively in the same manner as described for 3a.
3b (trans): Yield: 0.100 g (83%); yellow oil; 1H NMR (CDCl3, ꢁ, 300 MHz): 1.41±1.46 (m, 2H, 1
piperidyl -CH2-), 1.52±1.67 (m, 4H, 2 piperidyl -CH2-), 1.95±2.04 (m, 2H, -CH2-Bz), 2.31±2.60 (m,
6H, 2 piperidyl -N-CH2-, -CH2-N-), 2.70±2.77 (m, 2H, -CH2-Ph), 3.48 (dt, 1H, J 5.3, 6.2 Hz, H-3),
3.4±3.6 (1H, -OH), 3.71 (ddd, 1H, J 3.8, 6.4, 10.0 Hz, 1H, -CH(OH)-), 4.41 (dd, 1H, J 4.9,
6.4 Hz, H-2), 6.78 (d, 1H, J 7.9 Hz, arom H), 6.86 (dt, 1H, J 0.9, 7.5 Hz, arom H), 7.09±7.30 (m,
7H, arom H) ppm; 13C NMR (CDCl3, ꢁ, 75.4 MHz): 24.15, 26.05 (3 piperidyl -CH2-), 32.76 (-CH2-
Ph), 37.56 (-CH2-Bz), 43.87 (C-3), 54.63 (2 piperidyl-N-CH2-), 60.43 (-CH2-N-), 67.65 (-CH(OH)-),
89.75 (C-2), 109.32, 120.44, 124.66, 125.82, 128.14, 128.34, 130.21, 141.82, 159.31 (arom C) ppm;
IR (KBr): v 3350 (s, O-H), 2934 2855 (s, C-H), 1598 (m, arom C-H), 1497, 1480 (s, aliph C-H),
1236 (s, C-O), 750 (s, arom C-H) cm 1; HRMS (70 eV): 351.220 (Æ5 ppm) (M , 3.5), 149.0 (33.9),
128.1 (6.5), 98.1 (100.0), 91.0 (17.3), 84.0 (68.8), 55.0 (22.3).
1
3c (cis) Yield: 0.024 g (47%); yellow oil; H NMR (CDCl3, ꢁ, 300 MHz): 1.43±1.50 (m, 2H, 1
piperidyl -CH2-), 1.56±1.70 (m, 4H, 2 piperidyl-CH2-), 1.96±2.21 (m, 2H, -CH2-Bz), 2.39±2.44 (m,