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G.-A. Lee et al. / Tetrahedron 70 (2014) 2956e2961
27.23 (CH2), 27.15 (CH2), 20.9 (CH3), 20.8 (CH3), 19.8 (CH2). MS m/z
(%) 370 (Mþ, 92), 170 (100). HRMS (EI) calcd for C28H34 m/z
370.2661 (Mþ), found 370.2652. Anal. Calcd for C28H34: C 90.75, H
9.25. Found: C 90.68, H 9.21. X-ray: CCDC 966896.
410.1570. Anal. Calcd for C26H28Cl2: C 75.91, H 6.86. Found: C 75.85,
H 6.53. X-ray: CCDC 966900.
4.6.6. 1,2-Di(4-fluorophenyl)tricyclo[8.3.1.03,9]tetradec-3(9)-ene
(2g). White solid. Yield: 1.21 g, 32%. Mp 154e155 ꢁC. IR (KBr, cmꢀ1
)
4.6.2. 1,2-Di(4-methoxyphenyl)tricyclo[8.3.1.03,9]tetradec-3(9)-ene
2918, 2903, 2837, 1599, 1509, 1502, 1447, 1237, 1219, 825, 808. 1H
NMR (300 MHz, CDCl3) 6.89e6.61 (m, 8H), 3.20 (s, 1H), 2.60e2.50
(m, 1H), 2.41e2.32 (m, 3H), 2.18e2.10 (m, 1H), 2.0e1.52 (m, 14H).
13C NMR (75 MHz, CDCl3)
160.9 (d, C, J¼242.1 Hz), 160.6 (d, C,
(2c). White solid. Yield: 2.7 g, 67%. Mp 147e148 ꢁC. IR (KBr, cmꢀ1
)
d
3005, 2924, 2914, 2887, 2843, 1612, 1512, 1468, 1444, 1254, 1032,
821. 1H NMR (300 MHz, CDCl3, 318 K)
d
6.86 (d, 2H, J¼8.7 Hz), 6.67
d
(d, 2H, J¼8.2 Hz), 6.57 (d, 2H, J¼8.7 Hz), 6.46 (d, 2H, J¼8.2 Hz), 3.68
(s, 3H), 3.65 (s, 3H), 3.16 (s, 1H), 2.58e2.49 (m, 1H), 2.48e2.29 (m,
3H), 2.16 (dd, 1H, J¼8.2, 14.5 Hz), 1.96e1.33 (m, 14H). 13C NMR
J¼242.1 Hz), 145.5 (d, C, J¼2.8 Hz), 138.4 (d, C, J¼2.7 Hz), 137.6 (C),
136.5 (C), 131.8 (CH),127.1 (d, CH, J¼7.3 Hz), 114.0 (d, CH, J¼20.8 Hz),
113.7 (d, CH, J¼21.2 Hz), 58.8 (CH), 41.2 (CH2), 40.6 (C), 39.0 (CH),
35.4 (CH2), 35.1 (CH2), 33.0 (CH2), 32.3 (CH2), 27.10 (CH2), 27.06
(CH2), 27.0 (CH2), 19.5 (CH2). MS m/z (%) 378 (Mþ, 48), 269 (100),
109 (53). HRMS (EI) calcd for C26H28F2 m/z 378.2159 (Mþ), found
378.2155. Anal. Calcd for C26H28F2: C 82.50, H 7.46. Found: C 82.31,
H 7.40. X-ray: CCDC 985976.
(75 MHz, CDCl3, 318 K)
d 157.4 (C), 157.1 (C), 142.6 (C), 138.1 (C),
135.9 (C), 135.2 (C), 131.1 (CH), 126.6 (CH), 112.9 (CH), 112.5 (CH),
59.1 (CH), 55.2 (CH3), 55.1 (CH3), 41.4 (CH2), 40.5 (C), 39.3 (CH), 35.5
(CH2), 35.2 (CH2), 33.0 (CH2), 32.6 (CH2), 27.3 (CH2), 27.23 (CH2),
27.15 (CH2),19.7 (CH2). MS m/z (%) 402 (Mþ, 75), 294 (100), 281 (78),
148 (50), 121 (86). HRMS (EI) calcd for C28H34O2, m/z 402.2559
(Mþ), found 402.2550. Anal. Calcd for C28H34O2: C 83.54, H 8.51.
Found: C 83.48, H 8.47. X-ray: CCDC 966897.
4.7. Synthesis of 1-(4-acetylphenyl)-6-bromocycloheptene
(7h)
4.6.3. 1,2-Di(4-thiomethylphenyl)tricyclo[8.3.1.03,9]tetradec-3(9)-ene
To a stirred solution of compound 3h (4.0 g, 18.7 mmol) in CH2Cl2
(50 mL) at 0 ꢁC was added bromine (1 mL, 18.7 mmol in 10 mL
CH2Cl2) dropwise from a dropping funnel. The mixture was stirred at
(2d). White solid. Yield: 2.65 g, 61%. Mp 119e120 ꢁC. IR (KBr, cmꢀ1
)
3088, 3067, 3032, 3011, 2988, 1594, 1489, 1443, 815. 1H NMR
(300 MHz, CDCl3, 318 K)
d
6.96 (d, 2H, J¼8.4 Hz), 6.86 (d, 2H,
0
ꢁC for 1 h and then warmed to room temperature and stirred for
J¼8.4 Hz), 6.84 (d, 2H, J¼7.9 Hz), 6.68 (d, 2H, J¼7.9 Hz), 3.18 (s, 1H),
2.58e2.51 (m, 1H), 2.48e2.30 (m, 3H), 2.36 (s, 3H), 2.33 (s, 3H), 2.15
1 h. The solvent was removed on a rotary evaporator and added 0.1 g
silica gel. The mixture was stirred at room temperature for 72 h and
the crude material was purified by flash chromatography (hexane) to
give white solid 7g (4.1g, 75%). Mp 62e62.5 ꢁC. IR (KBr, cmꢀ1) 3039,
3003, 2951, 2929, 2906, 2848, 1671, 1600, 1407, 1357, 822. 1H NMR
(dd, 1H, J¼8.5, 15.2 Hz), 1.96e1.84 (3H, m), 1.82e1.29 (11H, m). 13
C
NMR (75 MHz, CDCl3, 318 K)
d 147.3 (C), 140.2 (C), 137.6 (C), 136.5
(C), 134.8 (C), 134.5 (C), 130.8 (CH), 126.9 (CH), 126.4 (CH), 126.2
(CH), 59.3 (CH), 41.2 (CH2), 40.9 (C), 39.2 (CH), 35.5 (CH2), 35.2
(CH2), 33.0 (CH2), 32.4 (CH2), 27.22 (CH2), 27.18 (CH2), 27.1 (CH2),
19.7 (CH2), 16.8 (CH3), 16.6 (CH3). MS m/z (%) 438, (Mþþ4, 0.4), 436
(Mþþ2, 13), 434 (Mþ, 100), 310 (55), 297 (62), 137 (43). HRMS (EI)
calcd for C28H34S2 m/z 434.2102 (Mþ), found 434.2099. Anal. Calcd
for C28H34S2: C 77.36, H 7.88. Found: C 77.39, H 7.87. X-ray: CCDC
966898.
(300 MHz, CDCl3)
J¼7.0), 4.40e4.32 (m, 1H), 3.33e3.21 (m, 2H), 2.59 (s, 3H), 2.57e2.48
(m, 1H), 2.38e2.26 (m, 3H), 1.89e1.77 (m, 1H), 1.61e1.48 (m, 1H). 13
NMR (75 MHz, CDCl3) 197.6 (C), 148.3 (C), 140.3 (C), 135.5 (C), 134.4
d
7.90 (d, 2H, J¼8.5), 7.41 (d, 2H, J¼8.5), 6.35 (t, 1H,
C
d
(CH), 128.6 (CH), 126.0 (CH), 51.5 (CH), 43.8 (CH2), 42.5 (CH2), 28.2
(CH2), 26.6 (CH3), 25.6 (CH2). MS m/z (%) 294 (Mþþ2, 60), 292 (Mþ,
60), 213 (100),169 (55). HRMS (EI) calcd for C15H17BrO, m/z 292.0463
(Mþ), found 292.0471. Anal. Calcd for C15H17BrO: C 61.45, H 5.84.
Found: C 61.64, H 6.16.
4.6.4. 1,2-Di(4-bromophenyl)tricyclo[8.3.1.03,9]- tetradec-3(9)-ene
(2e). White solid. Yield: 2.9 g, 58%. Mp 144e145 ꢁC. IR (KBr,
cmꢀ1) 3082, 3023, 2925, 2847, 1586, 1484, 1450, 1010, 818. 1H NMR
4.8. Synthesis of 6-bromo-1-(o-tolyl)cycloheptene (7i)
(300 MHz, CDCl3, 318 K)
d
7.16 (d, 2H, J¼8.6 Hz), 7.06 (d, 2H,
J¼8.1 Hz), 6.82 (d, 2H, J¼8.6 Hz), 6.65 (d, 2H, J¼8.1 Hz), 3.19 (s, 1H),
To a stirred solution of compound 3i (4.0 g, 21.5 mmol) in CH2Cl2
(50 mL) at 0 ꢁC was added bromine (1.1 mL, 21.5 mmol in 10 mL
CH2Cl2) dropwise from a dropping funnel. The mixture was stirred
at 0 ꢁC for 1 h and then warmed to room temperature and stirred
for 1 h. The solvent was removed on a rotary evaporator and added
0.1 g silica gel. The mixture was stirred at room temperature for
72 h and the crude material was purified by flash column chro-
matography (hexane) to give colorless oil 7h (4.7g, 82%). IR (KBr,
cmꢀ1) 3059, 3016, 2928, 2853, 1484, 1443, 1378, 752. 1H NMR
2.59e2.52 (m, 1H), 2.44e2.26 (m, 3H), 2.17 (dd, 1H, J¼8.5, 14.4 Hz),
1.99e1.26 (m, 14H). 13C NMR (75 MHz, CDCl3, 318 K)
d 148.6 (C),
141.6 (C), 137.2 (C), 136.8 (C), 132.0 (CH), 130.6 (CH), 130.2 (CH),
127.6 (CH), 119.6 (C), 119.2 (C), 58.9 (CH), 41.3 (CH2), 40.9 (C), 39.1
(CH), 35.4 (CH2), 35.1 (CH2), 32.9 (CH2), 32.2 (CH2), 27.09 (CH2),
27.07, (CH2), 19.6 (CH2). MS m/z (%) 502 (Mþþ4, 34), 500 (Mþþ2,
67), 498 (Mþ, 35), 331 (99), 329 (100). HRMS (EI) calcd for
C
C
26H28Br2 m/z 498.0558 (Mþ), found 498.0549. Anal. Calcd for
26H28Br2: C 62.42, H 5.64. Found: C 62.25, H 5.75. X-ray: CCDC
(300 MHz, CDCl3)
d
7.16e7.07 (m, 4H), 5.90 (td, 1H, J¼6.7, 1.5 Hz),
966899.
4.33 (tdd, 1H, J¼10.5, 3.3, 2.1 Hz), 3.22 (dd, 1H, J¼14.4, 11.0 Hz), 2.98
(td, 1H, J¼14.4, 2.1 Hz), 2.67e2.57 (m, 1H), 2.34e2.21 (m, 3H), 2.28
(s, 3H), 1.91e1.80 (m, 1H), 1.63e1.49 (m, 1H). 13C NMR (75 MHz,
4.6.5. 1,2-Di(4-chlorophenyl)tricyclo[8.3.1.03,9]tetradec-3(9)-ene
(2f). White solid. Yield: 1.7 g, 41%. Mp 125e126 ꢁC. IR (KBr, cmꢀ1
)
CDCl3) d 145.1 (C), 141.8 (C), 134.6 (C), 133.4 (CH), 130.2 (CH), 128.6
3091, 3020, 2921, 2893, 2849, 1594, 1487, 1450, 1441, 817. 1H NMR
(300 MHz, CDCl3, 318 K)
(CH), 126.9 (CH), 125.8 (CH), 52.0 (CH), 45.2 (CH2), 44.4 (CH2), 28.0
(CH2), 27.0 (CH2), 20.3 (CH3). MS m/z (%) 266 (Mþþ2, 77), 264 (Mþ,
80), 185 (100), 105 (91). HRMS (EI) calcd for C14H17Br, m/z 264.0514
(Mþ), found 264.0511. Anal. Calcd for C14H17Br: C 63.41, H 6.46.
Found: C 63.54, H 6.50.
d
7.0 (d, 2H, J¼8.7 Hz), 6.90 (d, 2H,
J¼8.0 Hz), 6.86 (d, 2H, J¼8.7 Hz), 6.71 (d, 2H, J¼8.0 Hz), 3.20 (s, 1H),
2.60e2.52 (m, 1H), 2.45e2.27 (m, 3H), 2.17 (dd, 1H, J¼8.4, 14.4 Hz),
2.0e1.27 (m, 14H). 13C NMR (75 MHz, CDCl3, 318 K)
d 148.2 (C), 141.2
(C), 137.3 (C), 136.8 (C), 131.5 (CH), 131.4 (C), 131.0 (C), 127.6 (CH),
127.3 (CH), 127.2 (CH), 59.0 (CH), 41.3 (CH2), 40.9 (C), 39.1 (CH), 35.4
(CH2), 35.1 (CH2), 32.9 (CH2), 32.3 (CH2), 27.1 (CH2), 19.6 (CH2). MS
m/z (%) 414 (Mþþ4, 3), 412 (Mþþ2, 16), 410 (Mþ, 25), 152 (69), 125
(100). HRMS (EI) calcd for C26H28Cl2 m/z 410.1568 (Mþ), found
Acknowledgements
Financial support from the National Science Council of the Re-
public of China (NSC 102-2113-M-030-007-MY2) and the National