Z. Liang et al. / Tetrahedron 63 (2007) 977–985
983
1.22 mmol), and allyl bromide (147 mg, 1.21 mmol) in
DMF (5 mL) afforded 12a (115 mg, 29%), 13 (120 mg,
34%), and 11 (114 mg, 37% recovered) after being stirred
for 19 h at rt. Compound 13: mp 41–42 ꢀC (ethyl ether/
petroleum ether). 1H NMR (300 MHz, CDCl3) d 6.93
(s, 1H), 6.76 (s, 1H), 6.11–5.98 (m, 1H), 5.44 (dm, J¼
17.1 Hz, 1H), 5.41 (s, 1H), 5.26 (dm, J¼10.2 Hz, 1 Hz),
4.50 (d, J¼4.8 Hz, 2H), 2.47 (q, J¼7.2 Hz, 4H), 1.66–1.43
(m, 8H), 0.95 (t, J¼6.9 Hz, 3H), 0.93 (t, J¼7.2 Hz, 3H);
13C NMR (75 MHz, CDCl3) d 152.5, 150.5, 133.2, 118.8,
117.2, 115.6, 115.5, 109.7, 98.8, 96.2, 76.3, 74.6, 70.3,
30.71, 30.69, 22.1, 21.9, 19.4, 19.3, 13.62, 13.59; MS (EI)
m/z (%): 310 (M+, 39.6), 41 (100.0); IR (neat) n (cmꢁ1):
3514, 2958, 2931, 2229, 1494. Anal. Calcd for C21H26O2:
C, 81.25; H, 8.44. Found: C, 81.42; H, 8.73.
gave 16b (35 mg, 88%) as a yellow oil. 1H NMR (300 MHz,
CDCl3) d 6.98 (s, 1H), 6.66 (s, 1H), 5.94 (t, J¼5.7 Hz, 2H),
4.93–4.90 (m, 2H), 4.86–4.84 (m, 2H), 4.30 (t, J¼6.0 Hz,
4H), 2.36 (q, J¼5.8 Hz, 4H), 2.07 (t, J¼6.9 Hz, 4H), 1.34–
1.16 (m, 8H), 0.80 (t, J¼6.9 Hz, 6H); 13C NMR (75 MHz,
CDCl3) d 157.5, 151.0, 141.6, 132.9, 125.4, 125.3, 114.2,
113.5, 75.9, 35.0, 30.2, 30.1, 22.3, 14.0; MS (EI) m/z (%):
378 (M+, 87.2), 335 (95.6), 321 (100.0); IR (neat)
n (cmꢁ1): 2958, 2931, 1602, 1493, 1125. HRMS Calcd for
C26H34O2: 378.2559. Found: 378.2546.
3.2.3. 6,8-Bis(10-butylethenyl)-2,3,4,10,11,12-hexahydro-
1,13-dioxabenzo[1,2-b:5,4-b0]-dicyclooctene (16c). A so-
lution of 4c (55 mg, 0.14 mmol) and the catalyst 15 (6 mg,
0.007 mmol) in CH2Cl2 (7 mL) was refluxed for 17 h under
Ar, then extra amount of 15 (9 mg, 0.11 mmol) was added,
which was followed by stirring under refluxing for another
10 h. Evaporation and flash column chromatography on
silica gel (petroleum ether/ethyl ether¼100:1) gave 16c
(40 mg, 73%) as a yellow oil. 1H NMR (300 MHz, CDCl3)
d 6.82 (s, 1H), 6.80 (s, 1H), 6.00 (t, J¼7.8 Hz, 2H), 4.92 (s,
2H), 4.76 (d, J¼1.5 Hz, 2H), 4.22–4.10 (br s, 4H), 2.22 (t,
J¼7.5 Hz, 4H), 2.16–2.00 (m, 4H), 1.74–1.64 (m, 4H),
1.47–1.39 (m, 4H), 1.37–1.25 (m, 4H), 0.88 (t, J¼6.9 Hz,
6H); 13C NMR (75 MHz, CDCl3) d 159.0, 149.5, 138.4,
132.1, 127.0, 126.6, 115.0, 113.8, 73.8, 33.9, 30.3, 26.8,
26.5, 22.4, 13.9; MS (EI) m/z (%): 406 (M+, 21.8),
363 (34.7), 84 (100.0); IR (neat) n (cmꢁ1): 2954, 2931,
1601, 1492, 1148. HRMS Calcd for C28H39O2 [M+H+]:
407.2945. Found: 407.2959.
3.1.17. 1-Allyloxy-4-(but-30-enyloxy)-2,5-bis(hex-10-ynyl)-
benzene (14). The reaction of 13 (120 mg, 0.39 mmol),
K2CO3 (215 mg, 1.56 mmol), and 3-butenyl bromide
(210 mg, 1.56 mmol) in DMF (3 mL) afforded 14 (124 mg,
88%) as an oil after being stirred for 10.5 h. 1H NMR
(300 MHz, CDCl3) d 6.86 (s, 1H), 6.85 (s, 1H), 6.11–5.85
(m, 2H), 5.44 (dm, J¼17.1 Hz, 1H), 5.26 (dm, J¼10.8 Hz,
1H), 5.16 (dm, J¼17.1 Hz, 1H), 5.09 (dm, J¼10.5 Hz,
1H), 4.52 (d, J¼5.1 Hz, 2H), 3.99 (t, J¼6.9 Hz, 2H), 2.55
(q, J¼6.8 Hz, 2H), 2.46 (t, J¼6.6 Hz, 2H), 2.45 (t, J¼
6.6 Hz, 2H), 1.65–1.45 (m, 8H), 0.94 (t, J¼7.5 Hz, 6H);
13C NMR (75 MHz, CDCl3) d 153.4, 153.0, 134.5, 133.2,
117.6, 117.5, 117.1, 116.9, 114.06, 113.97, 95.9, 95.8,
77.0, 76.6 (overlap with the signal of CDCl3), 70.1, 68.8,
33.8, 30.8, 30.7, 22.0, 21.9, 19.44, 19.41, 13.6; MS (EI)
m/z (%): 364 (M+, 18.7), 55 (100.0); IR (neat) n (cmꢁ1):
2957, 2932, 2222, 1500, 1405. HRMS Calcd for
C25H32O2Na+ [M+Na+]: 387.2295. Found: 387.2302.
3.2.4. 4,6-Bis(10-benzyloxymethylethenyl)-2,8-dihydro-
benzo[1,2-b:5,4-b0]dipyran (17a). A solution of 8a (55 mg,
0.12 mmol) and the catalyst 15 (6 mg, 0.007 mmol) in
CH2Cl2 (5 mL) was refluxed for 6 h under Ar. Evaporation
and flash column chromatography on silica gel (petroleum
ether/ethyl ether¼10:1) gave 17a (43 mg, 78%) as a
3.2. Intramolecular double ring-closing enyne metathesis
1
3.2.1. 4,6-Bis(10-butylethenyl)-2,8-dihydrobenzo-[1,2-
b:5,4-b0]dipyran (16a). Typical procedure C. To a solution
of 4a (63 mg, 0.18 mmol) in CH2Cl2 (6 mL) was added the
catalyst 15(8 mg, 0.009 mmol). After being refluxed with stir-
ringunder Arfor 8 h, the reactionwas complete(monitored by
TLC). Evaporation and flash columnchromatographyonsilica
gel (petroleum ether/ethyl ether¼100:1) gave 16a (48 mg,
76%) as a yellow oil. 1H NMR (300 MHz, CDCl3) d 6.87 (s,
1H), 6.38 (s, 1H), 5.51 (t, J¼4.2 Hz, 2H), 5.11–5.07 (m,
2H), 5.01–4.98 (m, 2H), 4.71 (d, J¼3.9 Hz, 4H), 2.20 (t, J¼
6.6 Hz, 4H), 1.41–1.21 (m, 8H), 0.88 (t, J¼7.2 Hz, 6H); 13C
NMR (75 MHz, CDCl3) d 155.5, 147.1, 137.6, 122.6, 116.5,
115.6, 114.3, 104.2, 65.4, 35.5, 30.2, 22.3, 13.9; MS (EI)
m/z (%): 350 (M+, 100.0), 307 (93.7), 293 (64.7); IR (neat) n
(cmꢁ1): 2957, 2930, 1619, 1490, 1159. HRMS Calcd for
C24H30O2: 350.2246. Found: 350.2242.
yellow oil. H NMR (300 MHz, CDCl3) d 7.39–7.21 (m,
10H), 6.97 (s, 1H), 6.43 (s, 1H), 5.64 (t, J¼3.6 Hz, 2H),
5.75 (s, 2H), 5.22 (s, 2H), 4.73 (d, J¼3.9 Hz, 4H), 4.53 (s,
4H), 4.09 (s, 4H); 13C NMR (75 MHz, CDCl3) d 155.7,
142.7, 138.1, 134.9, 128.3, 127.5, 122.0, 117.0, 116.4,
116.3, 104.4, 72.1, 71.8, 65.3; MS (MALDI) m/z (%):
478.1 (M+); IR (neat) n (cmꢁ1): 1619, 1493, 1159. HRMS
Calcd for C32H30O4Na+ [M+Na+]: 501.2036. Found:
501.2054.
3.2.5. 5,7-Bis(10-benzyloxymethylethenyl)-2,3,9,10-tetra-
hydro-1,11-dioxabenzo-[1,2-b:5,4-b0] dicycloheptene
(17b). A solution of 8b (70 mg, 0.14 mmol) and the catalyst
15 (6 mg, 0.006 mmol) in CH2Cl2 (5 mL) was refluxed
for 12 h under Ar. Evaporation and flash column chromato-
graphy on silica gel (petroleum ether/ethyl ether¼10:1)
gave 17b (40 mg, 57%) as a yellow oil. 1H NMR
(300 MHz, CDCl3) d 7.30–7.18 (m, 10H), 7.07 (s, 1H),
6.72 (s, 1H), 6.09 (t, J¼6.6 Hz, 2H), 5.26 (s, 2H), 5.06 (s,
2H), 4.44 (s, 4H), 4.33 (t, J¼6.0 Hz, 4H), 4.03 (s, 4H), 2.34
(q, J¼6.0 Hz, 4H); 13C NMR (75 MHz, CDCl3) d 157.4,
146.1, 139.0, 138.3, 132.0, 128.3, 127.6, 127.5, 126.7,
125.6, 115.7, 114.9, 76.5, 72.0, 71.7, 29.7; MS (ESI) m/z
The following compounds were prepared according to
procedure C.
3.2.2. 5,7-Bis(10-butylethenyl)-2,3,9,10-tetrahydro-1,11-
dioxabenzo[1,2-b:5,4-b0]dicycloheptene (16b). A solution
of 4b (40 mg, 0.11 mmol) and the catalyst 15 (10 mg,
0.012 mmol) in toluene (10 mL) was stirred at 80 ꢀC for
13 h under ethylene. Evaporation and flash column chro-
matography on silica gel (petroleum ether/ethyl ether¼50:1)
(%): 524.1 (M+NH4 ); IR (neat) n (cmꢁ1): 1605, 1499,
+
1453, 1123, 1092. Anal. Calcd for C34H34O4Na+ [M+Na+]:
529.2349. Found: 529.2346.