4100
B. Lanta~no et al. / Tetrahedron 64 (2008) 4090e4102
(1H, dt, J¼3.8, 3.8, 10.5 Hz, CHCHCH2), 2.74 (1H, m,
ArCHCH), 2.93 (2H, m, CH2CH2Ar), 3.39 (3H, s, OCH3),
3.78 (3H, s, OCH3), 3.84 (3H, s, OCH3), 6.50 (1H, s, Ar),
7.11e7.21 (8H, m, Ar), 7.74 (1H, m, Ar). dC 10.9, 20.4, 23.8,
26.0, 45.3, 56.1, 56.5, 58.8, 59.7, 60.5, 102.2, 125.3, 126.0,
126.3, 127.3, 128.0, 128.5, 131.7, 134.4, 136.9, 140.1, 141.2,
142.2, 150.0, 150.5, 155.4. Anal. Calcd for C28H30O3: C,
81.1; H, 7.3. Found: C, 81.3; H, 7.4.
4.2.12. (4bS/R,9S/R,9aS/R)-5,6,7-Trimethoxy-9,4b-diphenyl-
10,11,4b,9a-tetrahydrobenzo[c]fluorene (36) and (4bS/R,
9R/S,9aS/R)-5,6,7-trimethoxy-9,4b-diphenyl-10,11,4b,9a-
tetrahydrobenzo[c]fluorene (37)
General procedure was carried out with alcohol 7 (0.12 g,
0.46 mmol), 4-phenyl-1,2-dihydronaphthalene 14 (0.10 g,
0.50 mmol), and SnCl4 (0.15 g, 0.30 mmol). p-TLC (CHCl3)
afforded 0.11 g (52%) of 36 and 37 as a 1:1.3 (36/37) mixture
and the same chromatographic system allowed the separation
of 36 (white solid), mp: 193e195 ꢁC, and 37 (white solid),
mp: 210e212 ꢁC. Major diastereomer 37: dH 1.5 (1H, m,
CH2), 1.6 (1H, m, CH2), 2.38 (1H, m, CHCHCH2), 2.61 (1H,
m, CHCH2Ar), 3.07 (1H, m, CHCH2Ar), 3.10 (3H, s, OCH3),
3.77 (3H, s, OCH3), 3.88 (3H, s, OCH3), 4.36 (1H, d,
J¼7.2 Hz, ArCHAr), 6.50 (1H, d, J¼0.8 Hz, Ar), 6.94 (2H,
m, Ar), 7.02e7.19 (4H, m, Ar), 7.20e7.29 (8H, m, Ar). dC
23.1, 28.6, 53.3, 56.0, 56.1, 56.5, 59.8, 60.8, 104.4, 124.9,
125.0, 125.9, 126.8, 127.4, 127.8, 128.0, 128.1, 129.9, 132.8,
133.0, 135.0, 136.8, 138.7, 140.7, 141.0, 149.0, 151.9, 153.4.
Minor diastereomer 36: dH 1.68 (2H, m, CH2), 2.81 (2H, m,
CH2CH2Ar), 3.10 (1H, m, CHCHCH2), 3.49 (3H, s, OCH3),
3.67 (3H, s, OCH3), 3.80 (3H, s, OCH3), 4.13 (1H, d,
J¼11.8 Hz, ArCHAr), 6.17 (1H, d, J¼0.8 Hz, Ar), 7.14e7.40
(13H, m, Ar), 7.86 (1H, m, Ar). dC 25.7, 28.5, 51.9, 56.1,
58.3, 59.8, 60.5, 62.2, 103.7, 125.5, 126.3, 126.6, 126.7,
127.5, 128.5, 128.6, 128.8, 128.9, 131.7, 132.4, 133.3, 137.9,
140.8, 143.0, 143.1, 149.4, 152.5, 153.9. Anal. Calcd for
C32H30O3: C, 83.1; H, 6.5. Found: C, 83.2; H, 6.6.
4.2.10. (4bR/S,9R/S,9aS/R)-9-Ethyl-6,7-dimethoxy-10,11,
4b,9a-tetrahydrobenzo[c]fluorene (31) and (4bR/S,9S/R,
9aS/R)-9-ethyl-6,7-dimethoxy-10,11,4b,9a-
tetrahydrobenzo[c]fluorene (32)
General procedure was carried out with alcohol 4 (0.17 g,
0.86 mmol), 1,2-dihydronaphthalene 15 (0.11 g, 0.85 mmol),
and SnCl4 (0.31 g, 1.20 mmol). p-TLC (80:20, hexane/ethyl
acetate) afforded 0.11 g (42%) of 31 and 32 as a 1:1.2 (31/
32) inseparable mixture (clear oil). Mixture diastereomer 31
and 32: dH 0.95 (3H, t, J¼7.4 Hz, CH3), 1.06 (3H, t,
J¼7.1 Hz, CH3), 1.65 (7H, m), 1.81 (1H, m), 2.55 (1H, m),
2.67 (2H, m), 2.75 (3H, m), 3.80 (3H, s, OCH3), 3.86 (6H,
s, OCH3), 3.88 (4H, overlaps with OCH3), 4.39 (1H, d,
J¼6.9 Hz, ArCHAr), 6.76 (6H, m, Ar), 7.15 (2H, m, Ar),
7.27 (3H, m, Ar), 7.41 (d, J¼7.7 Hz, Ar). dC 12.4, 13.8,
18.8, 20.6, 24.7, 27.4, 27.5, 28.6, 37.6, 42.6, 44.2, 46.2, 48.4,
52.7, 55.7, 55.8, 55.9, 56.0, 107.1, 107.8, 107.9, 108.3, 111.1,
111.7, 120.1, 125.6, 125.7, 125.8, 126.0, 135.3, 136.6, 136.7,
136.8, 137.2, 137.5, 137.7, 137.8, 138.0, 147.0, 147.6, 148.0,
148.7. Anal. Calcd for C21H24O2: C, 81.8; H, 7.8. Found: C,
81.9; H, 7.7.
4.2.13. (4bR/S,9S/R,9aS/R)-5,6,7-Trimethoxy-9-phenyl-
10,11,4b,9a-tetrahydrobenzo[c]fluorene (38) and (4bR/
S,9R/S,9aS/R)-5,6,7-trimethoxy-9-phenyl-10,11,4b,9a-
4.2.11. (5aR/S,5S/R,10bS/R,)-1,2,3-Trimethoxy-5-phenyl-
indano[1,2-a]indane (34) and (5R/S,5aR/S,10bS/R,)-
1,2,3-trimethoxy-5-phenylindano[1,2-a]indane (35)
tetrahydrobenzo[c]fluorene (39)
General procedure was carried out with alcohol 7 (0.11 g,
0.42 mmol), 1,2-dihydronaphthalene 15 (0.08 g, 0.67 mmol),
and SnCl4 (0.14 g, 0.54 mmol). p-TLC (CHCl3) afforded
0.03 g (20%) of 38 and 39 as a 1:1 (38/39) mixture (white
solid). p-TLC (70:30, hexane/ethyl acetate) allowed the sepa-
ration of 38 (white solid), mp: 79e80 ꢁC, and 39 (white solid),
mp: 58e60 ꢁC. Diastereomer 38: dH 1.72 (1H, m, J¼4.9, 5.1,
10.0, 15.3 Hz, CHCH2), 1.96 (1H, m, J¼5.1, 5.4, 10.0,
15.3 Hz, CH2), 2.73 (1H, m, J¼5.1, 5.4, 16.1 Hz, CHCH2Ar),
2.88 (1H, m, J¼5.1, 7.7, 10.2, 11.3 Hz, CHPhCHCH2), 2.95
(1H, m, J¼4.9, 10.0, 16.1 Hz, CHCH2Ar), 3.66 (3H, s,
OCH3), 3.90 (3H, s, OCH3), 4.02 (3H, s, OCH3), 4.04 (1H,
d, J¼11.3 Hz, ArCHPh), 4.50 (1H, d, J¼7.7 Hz, ArCHAr),
6.15 (1H, s, Ar), 7.14 (3H, m, Ar), 7.23 (3H, m, Ar), 7.33
(2H, m, Ar), 7.63 (1H, d, J¼7.2 Hz, Ar). dC 23.8, 27.1, 44.4,
50.5, 54.3, 56.3, 60.7, 61.0, 104.3, 125.8, 126.3, 128.2, 128.5,
128.7, 129.5, 129.8, 130.7, 137.3, 138.2, 140.7, 142.6, 143.2,
150.1, 153.3. Diastereomer 39: dH 1.28 (1H, m, CHCH2),
1.45 (1H, m, CHCH2), 2.51 (2H, m, CHCH2Ar, CHCH2Ar),
3.01 (1H, m, CHCH2Ar), 3.43 (3H, s, OCH3), 3.74 (3H, s,
OCH3), 3.87 (3H, s, OCH3), 4.45 (1H, d, J¼7.2 Hz, ArCHPh),
4.51 (1H, d, J¼7.7 Hz, ArCHAr), 6.48 (1H, s, Ar), 7.04e7.16
(4H, m, Ar), 7.19e7.26 (4H, m, Ar), 7.53 (1H, d, J¼7.4 Hz,
Ar). dC 22.9, 29.0, 45.3, 47.1, 55.4, 56.2, 60.5, 61.0, 104.6,
General procedure was carried out with alcohol 7 (0.13 g,
0.46 mmol), indene 13 (0.08 g, 0.74 mmol), and SnCl4
(0.15 g, 0.60 mmol). p-TLC (CHCl3) afforded 0.02 g (26%)
of 34 and 35 as a 1:1.2 (34/35) inseparable mixture (yellow
solid). Major diastereomer 35: dH 2.59 (2H, d, J¼7.5 Hz,
CHCH2Ar), 3.64 (1H, m, J¼7.5, 7.9, 8.8 Hz, CHPhCHCH2),
3.67 (3H, s, OCH3), 3.91 (4H, overlaps with OCH3, ArCHPh),
3.74 (3H, s, OCH3), 3.89 (3H, s, OCH3), 3.94 (3H, s, OCH3),
4.62 (1H, d, J¼8.8 Hz, ArCHAr), 6.42 (1H, s, Ar), 7.04 (3H,
m, Ar), 7.17e7.39 (5H, m, Ar), 7.67 (1H, d, J¼7.5 Hz, Ar). Mi-
nor diastereomer 34: dH 3.00 (1H, dd, J¼1.8, 16.2 Hz, CH2),
3.15 (1H, dd, J¼7.2, 16.2 Hz, CH2), 3.31 (1H, m, J¼1.8, 7.2,
7.5, 7.7 Hz, CHPhCHCH2), 3.66 (3H, s, OCH3), 3.90 (3H, s,
OCH3), 4.12 (3H, s, OCH3), 4.85 (1H, d, J¼7.7 Hz, ArCHPh),
4.92 (1H, d, J¼7.7 Hz, ArCHAr), 6.10 (1H, s, Ar), 6.88 (1H, d,
J¼7.5 Hz, Ar), 7.17e7.39 (7H, m, Ar), 7.58 (1H, m, Ar). Mix-
ture diastereomer 34 and 35: dC 34.1, 36.5, 49.2, 53.1, 54.0,
54.2, 55.3, 56.1, 58.1, 60.5, 60.7, 60.8, 60.9, 103.7, 104.4,
124.0, 125.0, 125.9, 126.0, 126.1, 126.3, 126.5, 126.6,
126.8, 126.9, 127.9, 128.6, 129.3, 141.8, 142.1, 143.4, 144.4.
Anal. Calcd for C25H24O3: C, 80.6; H, 6.5. Found: C, 80.7;
H, 6.6.