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Y.-Y. Lai et al. / Tetrahedron 63 (2007) 6051–6055
(d, J¼8.2 Hz, 1H), 2.04 (s, 3H), 2.84–2.87 (m, 2H), 2.88–
3.00 (m, 2H), 3.01–3.11 (m, 2H), 3.19–3.24 (m, 2H), 4.98
(s, 2H), 6.13 (s, 2H), 6.41 (d, J¼8.6 Hz, 2H), 7.20 (d, J¼
8.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 21.3, 45.5, 46.6,
50.5, 52.1, 66.9, 111.6, 122.0, 130.1, 135.6, 147.4, 170.9.
washed with DCM/NEt3 (10:1, 10 mLꢂ2) and the filtrate
was concentrated in vacuo to give the residue, which was
chromatographed on silica gel (hexane/EtOAc 7:1) to afford
17 as a white solid (220 mg, 70%); mp 82–83 ꢁC (lit.14 86.5–
87 ꢁC); 1H NMR (400 MHz, CDCl3) d 2.87 (s, 12H), 3.79 (s,
2H), 6.66 (d, J¼8.8 Hz, 2H), 7.03 (d, J¼8.8 Hz, 2H); 13C
NMR (100 MHz, CDCl3) d 39.9, 40.9, 112.8, 129.2, 130.1,
148.8. HRMS (FAB+) (C17H22N2) calcd: 254.1783; found:
254.1780.
2.3. Bis-{4-(4-aza-tricyclo[5.2.1.02,6]dec-8-en-4-yl)-
phenyl}methane (8)
To a DCM solution (60 mL) of 1113 (2 g, 8.3 mmol) and
DMAP (1.0 g, 8.3 mmol) was added slowly acetyl chloride
(0.65 g, 8.3 mmol) in DCM (20 mL) and the mixture was
stirred at rt for 24 h. Water (100 mL) was added and the
organic layer was separated and washed with brine, dried
(MgSO4), and filtered. The solvent was evaporated in vacuo
and the oily residue was dissolved in DCM (40 mL). Neutral
alumina (45 g) was added and the mixture was stirred at rt for
8 h. After filtration, solvent was removed in vacuo and the
residue was recrystallized from DCM/hexane to give 8
Acknowledgements
This work is supported by the National Science Council and
the National Taiwan University.
Supplementary data
1
(0.72 g, 40%); mp 188–189 ꢁC (dec); H NMR (400 MHz,
Supplementary data associated with this article can be found
CDCl3) d 1.50 (d, J¼8.2 Hz, 2H), 1.59 (d, J¼8.2 Hz, 2H),
2.85–2.88 (m, 4H), 2.95 (br s, 4H), 3.03–3.05 (m, 4H),
3.17–3.22 (m, 4H), 3.75 (s, 2H), 6.13 (m, 4H), 6.37 (d, J¼
8.5 Hz, 4H), 6.99 (d, J¼8.5 Hz, 4H); 13C NMR (100 MHz)
40.0, 45.5, 46.5, 50.7, 52.2, 111.9, 129.1, 129.3, 135.8,
146.0; IR (KBr) n 2964, 2942, 2864, 2833, 1688, 1615,
1518, 1473, 1432, 1369, 1341, 1201, 1186, 1134, 971, 904,
797, 776, 739, 717; MS (70 eV, EI) m/z (%) 434 (100)
[M+], 393 (18), 367 (82), 372 (13), 301 (52); HRMS
(FAB+) (C31H34N2) calcd: 434.2722; found: 434.2725.
References and notes
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From pure 12. Under N2, to a solution of 12 (500 mg,
1.8 mmol) in DCM (7 mL) was added Al2O3 (neutral, 8 g)
at rt. The mixture was stirred for 20 h at rt and then filtered.
The Al2O3 was washed with DCM/NEt3 (10:1) (10 mLꢂ2)
and the filtrate was concentrated in vacuo. The residue was
chromatographed on silica gel (hexane/EtOAc 7:1) to afford
8 as a white solid (230 mg, 62%); mp 188–189 ꢁC (dec).
ꢀ
L.; Mojovic, L.; Levacher, V.; Dupas, G.; Queguiner, G.;
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Under N2, to a solution of 12 (50 mg, 0.2 mmol) in MeOH
(5 mL) was added Al2O3 (neutral, 1 g) at rt. The mixture
was stirred for 20 h at rt and then filtered. The Al2O3 was
washed with DCM/NEt3 (10:1) (10 mLꢂ2) and the filtrate
was concentrated in vacuo. The residue was passed through
a silica gel bed (thickness¼5 cm) and washed with (hex-
ane/EtOAc (7:1, 20 mL). Evaporation of the solvent afforded
13 as a white solid (44 mg, 99%); mp 64–65 ꢁC (lit.11a 64–
1
65 ꢁC); H NMR (400 MHz, CDCl3) d 1.47 (dt, J¼1.6,
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ꢀ
ꢀ
ꢀ
8.0 Hz, 2H), 1.58 (dt, J¼1.6, 8.0 Hz, 2H), 2.81–2.84 (m,
2H), 2.90–2.96 (m, 2H), 2.98–3.06 (m, 2H), 3.15–3.22 (m,
2H), 3.21 (s, 3H), 4.30 (s, 2H), 6.10 (s, 2H), 6.38 (d, J¼
8.6 Hz, 2H), 7.12 (d, J¼8.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3) d 45.4, 46.4, 50.5, 52.0, 57.2, 74.6, 111.4, 124.3,
129.1, 135.5, 147.0.
^
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Under N2, to a solution of 16 (500 mg, 1.8 mmol) in DCM
(12 mL) was added Al2O3 (neutral, 14 g) at rt. The mixture
was stirred for 20 h at rt and then filtered. The Al2O3 was