F. C. Zacconi et al. / Tetrahedron: Asymmetry 22 (2011) 40–46
45
Elemental Anal. Calcd for C36H30O4: C, 82.11; H, 5.74. Found: C,
82.00; H, 5.69.
330 (6), 230 (6), 215 (7), 202 (5), 178 (100), 152 (7), 83 (57), 55
(52); HRMS (ESI) m/z calcd for C28H30O4 [M]+Å 430.2144, found:
430.214.
4.10.4. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethano anthra-
cene-11,12-dimethyl bis((E)-2-butenoate) 15
4.10.8. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethano anthra-
cene-11,12-dimethyl bis(propenoate) 20
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 70:30) to give 15 (0.35 g,
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 70:30) to give 20 (3.87 g,
0.88 mmol, 94%) as a yellowish dense oil, ½a D23
¼ ꢀ13:7 (c 1.00,
ꢂ
CH2Cl2); 1H NMR: 1.79 (dd, 6H, 4J = 1.5 Hz, 3J = 6.3 Hz), 2.01–2.09
(m, 2H), 3.57 (dd, 2H, 3J = 8.6 Hz, 2J = 11.1 Hz), 3.78 (dd, 2H,
3J = 5.7 Hz, 2J = 11.1 Hz), 4.17 (s, 2H), 5.77 (dq, 2H, 3J = 15.7 Hz,
3J = 6.3 Hz), 6.87 (dq, 2H, 3J = 15.7 Hz, 4J = 1.5 Hz), 6.96–7.23 (m,
8H); 13C NMR: 18.46, 42.94, 46.53, 66.95, 122.96, 123.9, 125.89,
10.33 mmol, 70%) as a white solid, mp: 92–94 °C; ½a D23
¼ ꢀ19:2 (c
ꢂ
1.00, CH2Cl2); 1H NMR: 1.68–1.82 (m, 2H), 3.61 (dd, 2H,
3J = 7.6 Hz, 2J = 11.3 Hz), 3.83 (dd, 2H, 3J = 4.8 Hz, 2J = 11.3 Hz),
4.17 (s, 2H), 5.73 (dd, 2H, 2J = 1.5 Hz, 3J = 10.0 Hz), 6.05 (dd, 2H,
2J = 1.5 Hz, 3J = 10.5 Hz), 6.30 (dd, 2H, 3J = 10 Hz, 3J = 10.5 Hz),
6.94–7.30 (m, 8H); 13C NMR: 42.85, 46.35, 67.15, 123.94, 125.93,
126.54, 126.78, 128.78, 131.36, 140.58, 143.37, 166.25; IR (KBr)
126.41, 126.68, 140.61, 143.45, 145.39, 166.61; IR (neat) m: 3072,
3041, 3017, 2940, 2913, 1720, 1654, 1460, 1441, 1258, 1177,
1099, 959, 839, 757, 730 cmꢀ1; MS: m/z (%) 402 (13), 178 (100),
69 (32); HRMS (ESI) m/z calcd for C26H26O4 [M]+Å 402.1831, found:
402.183.
m
: 3068, 3041, 3017, 2955, 2893, 1732, 1631, 1468, 1410, 1297,
1270, 1192, 1188, 1056, 982, 908, 811, 757, 730 cmꢀ1; MS: m/z
(%) 374 (13), 215 (2), 202 (3), 178 (100), 152 (3), 97(3), 83 (3), 55
(20); HRMS (ESI) m/z calcd for C24H22O4 [M]+Å 374.1518, found:
374.152. Elemental Anal. Calcd for C24H22O4: C, 76.99; H, 5.92.
Found: C, 77.08; H, 5.98.
4.10.5. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethanoanthra-
cene-11,12-dimethyl bis((E)-2-methyl-3-phenylpropenoate) 17
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 70:30) to give 17 (0.49 g,
4.10.9. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethanoanthra-
cene-11,12-dimethyl bis((E)-3-methyl-2-butenoate) 21
0.88 mmol, 94%) as a white solid, mp: 73–75 °C; ½a D23
¼ þ7:3 (c
ꢂ
1.06, CH2Cl2); 1H NMR: 1.81–1.89 (m, 2H), 2.01 (s, 6H), 3.69 (dd,
2H, 3J = 8.1 Hz, 2J = 11.3 Hz), 3.92 (dd, 2H, 3J = 5.5 Hz, 2J = 11.3 Hz),
4.19 (s, 2H), 6.99 (m, 2H), 7.11–7.34 (m, 8H), 7.60 (s, 10H); 13C
NMR: 14.61, 43.11, 46.75, 67.77, 124.04, 126.02, 126.63, 126.82,
128.86, 130.22, 136.36, 139.71, 140.76, 143.54, 168.73; IR (KBr)
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 75:25) to give 21 (0.34 g,
0.84 mmol, 89%) as a yellowish dense oil, ½a D23
¼ ꢀ18:9 (c 1.00,
ꢂ
CH2Cl2), 1H NMR 1.68–1.70 (m, 2H), 1.78 (s, 6H), 2.06 (s, 6H),
3.50 (dd, 2H, 3J = 7.4 Hz, 2J = 11.3 Hz), 3.75 (dd, 2H, 3J = 5.2 Hz,
2J = 11.3 Hz), 4.17 (s, 2H), 5.62 (s, 2H), 6.91–7.24 (m, 8H); 13C
NMR: 20.63, 27.75, 43.03, 46.43, 66.34, 116.36, 123.90, 125.88,
m
: 3060, 3017, 2951, 2889, 1701, 1631, 1491, 1445, 1250, 1196,
1114, 909, 757, 730, 699 cmꢀ1; MS: m/z (%) 554 (3), 230 (25),
215 (20), 202 (9), 178 (100), 152 (9), 145 (70), 117 (73), 91 (49),
77 (4); HRMS (ESI) m/z calcd for C38H34O4 [M]+Å 554.2457, found:
554.245. Elemental Anal. Calcd for C38H34O4: C, 82.28; H, 6.18.
Found: C, 82.36; H, 6.24.
126.40, 126.64, 140.75, 143.48, 157.27, 166.71; IR (neat) m: 3064,
3037, 3021, 2944, 2909, 1709, 1650, 1445, 1227, 1142, 1076,
912, 846, 757, 730 cmꢀ1, MS: m/z (%) 430 (6), 178 (100), 152 (2),
83 (19), 55 (8), HRMS (ESI) m/z calcd for
C
28H30O4 [M]+Å
430.2144, found: 430.214.
4.10.6. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethanoanthra-
cene-11,12-dimethyl bis((E)-2,3-diphenyl-2-propenoate) 18
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 81:15) to give 18 (0.48 g,
4.10.10. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethano
anthracene-11,12-dimethyl bis(phenylpropynoate) 23
Method A. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 70:30) to give 23 (0.77 g,
0.70 mmol, 75%) as a white solid, mp: 69–71 °C; ½a D23
¼ ꢀ4:1 (c
ꢂ
1.06, CH2Cl2); 1H NMR: 1.52–1.63 (m, 2H), 3.46 (dd, 2H,
3J = 7.5 Hz, 2J = 11.2 Hz), 3.65 (dd, 2H, 3J = 4.7 Hz, 2J = 11.2 Hz),
3.89 (s, 2H), 6.90–7.40 (m, 28H), 7.75 (s, 2H); 13C NMR: 42.54,
46.13, 67.70, 123.86, 125.84, 126.45, 126.65, 128.30, 128.68,
129.14, 129.57, 130.13, 131.17, 133.05, 135.03, 136.64, 140.57,
1.47 mmol, 87%) as a yellowish dense oil; ½a D23
¼ þ7:4 (c 0.98,
ꢂ
CH2Cl2); 1H NMR: 1.92–2.10 (m, 2H), 3.91 (dd, 2H, 3J = 8.9 Hz,
2J = 11.3 Hz), 4.14 (dd, 2H, 3J = 5.4 Hz, 2J = 11.3 Hz), 4.48 (s, 2H),
7.17–7.83 (m, 18H); 13C NMR: 42.62, 46.07, 68.33, 81.00, 87.25,
120.00, 124.13, 126.07, 126.68, 126.97, 129.04, 131.17, 133.48,
140.85, 143.21, 167.71; IR (film)
m: 3052, 3021, 2951, 2889, 1709,
140.33, 143.12, 154.20 ppm; IR (neat) m: 3064, 3017, 2920, 2850,
1627, 1491, 1445, 1250, 1165, 909, 761, 734, 707, 687 cmꢀ1; MS:
m/z (%) 678 (4), 277 (14), 230 (23), 215 (17), 207 (40), 202 (11),
178 (100), 152 (28), 77 (12); HRMS (ESI) m/z calcd for C48H38O4
[M]+Å 678.2770, found: 678.276. Elemental Anal. Calcd for
2221, 1709, 1487, 1456, 1281, 1184, 1165, 905, 757, 730,
687 cmꢀ1; MS: m/z (%) 552 (18), 231 (2), 202 (4), 178 (100), 152
(3), 129(30), 102(3), 75 (4); HRMS (ESI) m/z calcd for C36H26O4
[M]+Å 522.1831, found: 522.183.
C48H38O4: C, 84.93; H, 5.64. Found: C, 85.02; H, 5.68.
4.10.11. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethano
anthracene-11,12-dimethyl bis(2-octynoate) 24
4.10.7. Synthesis of (11R,12R)-9,10-dihydro-9,10-ethano anthra-
cene-11,12-dimethyl bis((E)-2-methyl-2-butenoate) 19
Method A. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 80:20) to give 24 (0.43 g,
Method B. The crude product was purified by column chroma-
tography (Silica Gel 60, hexane–Et2O, 80:20) to give 19 (0.31 g,
0.85 mmol, 90%) as a yellowish dense oil, ½a D23
¼ ꢀ8:1 (c 1.00,
ꢂ
0.71 mmol, 76%) as a yellowish dense oil; ½a D23
ꢂ
¼ ꢀ18:8 (c 1.00,
CH2Cl2); 1H NMR: 0.83 (t, 6H), 1.15–1.38 (m, 8H), 1.44–1.58 (m,
4H), 1.62–1.73 (m, 2H), 2.24 (t, 4H), 3.53 (dd, 2H, 3J = 8.4 Hz,
2J = 11.3 Hz), 3.80 (dd, 2H, 3J = 5.1 Hz, 2J = 11.3 Hz), 4.19 (s, 2H),
6.94–7.31 (m, 8H); 13C NMR: 14.24, 19.11, 22.46, 27.60, 31.44,
42.56, 45.96, 67.98, 73.46, 90.64, 123.95, 125.92, 126.59, 126.78,
CH2Cl2); 1H NMR (300 MHz, CDCl3) d (ppm) 1.85–2.06 (m, 14H),
3.79 (dd, 2H, 3J = 8.1 Hz, 2J = 11.2 Hz), 4.06 (dd, 2H, 3J = 5.3 Hz,
2J = 11.2 Hz), 4.39 (s, 2H), 6.71 (m, 2H), 6.92–7.40 (m, 8H); 13C
NMR (300 MHz, CDCl3) d (ppm) 12.41, 14.73, 42.88, 46.57, 67.13,
123.87, 125.81, 126.6, 128.5, 137.89, 140.06, 140.73, 141.95,
140.39, 143.22, 154.00; IR (neat)
2858, 2229, 1712, 1460, 1235, 1080, 955, 746, 726, 629 cmꢀ1
MS: m/z (%) 510 (7), 231(6), 215 (8), 202 (6), 178 (100), 152 (5),
m: 3068, 3045, 3021, 2928,
143.46, 168.12; IR (neat)
m
: 3068, 3017, 2924, 2854, 1713, 1650,
;
1456, 1266, 1142, 1076, 761, 734 cmꢀ1; MS: m/z (%) 430 (25),