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F. C. E. Saraber et al. / Tetrahedron 62 (2006) 1726–1742
1734
(CDCl3) d: 14.7 (q), 17.2 (q), 21.6 (q), 25.3 (t), 26.7 (t), 28.8
(t), 31.0 (t), 40.5 (d), 41.3 (d), 43.4 (t), 47.5 (d), 51.0 (s),
55.5 (q), 63.0 (d), 94.4 (d), 110.9 (t), 112.2 (d), 113.5 (d),
125.4 (s), 128.0 (2d), 128.1 (d), 128.7 (2d), 130.8 (d), 136.1
(s), 144.4 (s), 147.3 (s), 155.6 (s), 163.4 (s), 198.5 (s), 214.8
(s). HRMS: MC, found 486.2771. C32H38O4 requires
486.2770. MS m/e (%) 486 (MC, 8), 457 (10), 440 (2),
336 (40), 335 (39), 308 (23), 179 (34), 161 (100), 133 (30),
105 (33), 55 (20).
compound 29 as a slightly yellow oil (22 mg, 23%) and
compound 28 (48 mg, 46%), which rapidly cyclized to 29
upon evaporation of the solvent, next to some remaining
starting material 27b. 1H NMR (C6D6) d: 1.01 (s, 3H), 1.50–
2.70 (m, 10H), 1.65 (s, 3H), 3.15–3.30 (m, 1H), 3.43 (s, 6H),
4.18 (dd, J1Z4.2 Hz, J2Z11.9 Hz, 1H), 5.02 (s, 1H), 5.07
(s, 1H), 5.35 (dd, J1Z2.4 Hz, J2Z5.7 Hz, 1H), 6.77 (dd,
J1Z2.6 Hz, J2Z8.4 Hz, 1H), 6.85 (d, JZ2.6 Hz, 1H), 7.05–
7.35 (m, 3H), 7.43 (d, J1Z8.4 Hz, 1H), 7.79 (d, J1Z9.7 Hz,
2H); 13C NMR (C6D6) d: 12.9 (q), 22.6 (q), 26.9 (t), 28.5 (t),
29.3 (2t), 36.5 (t), 37.0 (s), 38.9 (d), 39.0 (d), 54.6 (q), 58.8
(q), 77.4 (d), 97.0 (d), 111.1 (d), 111.3 (t), 113.8 (d), 122.4
(s), 123.8 (d), 124.5 (2d), 127.5 (2d), 128.4 (d), 136.3 (s),
139.4 (s), 146.1 (2s), 149.9 (s), 150.6 (s), 159.1 (s). HRMS:
MC, found 456.2658. C31H36O3 requires 456.2664. MS m/e
(%) 456 (MC, 100), 441 (26), 308 (23), 269 (17), 216 (28),
105 (35).
Isomer 27b. White crystals (mp 119–123 8C, from hexane/
ethyl acetate). IR (CCl4 sol.) cmK1: 2976, 2938, 2875, 1704,
1679, 1602, 1249; 1H NMR (CDCl3) d: 1.06 (s, 3H), 1.26 (d,
JZ7.2 Hz, 1H), 1.32 (t, JZ6.9 Hz, 3H), 1.62 (s, 3H), 1.60–
3.25 (m, 12H), 3.80 (q obsc., JZ6.9 Hz, 2H), 3.84 (s obsc.,
3H), 4.51 (dd, J1Z5.9 Hz, J2Z9.3 Hz, 1H), 4.62 (s, 1H),
4.77 (s, 1H), 6.60 (d, JZ2.5 Hz, 1H), 6.82 (dd, JZ2.5,
8.7 Hz, 1H), 7.05–7.55 (m, 5H), 7.99 (d, JZ8.7 Hz, 1H);
13C NMR (CDCl3) d: 14.8 (q), 20.7 (q), 20.8 (q), 26.4 (t),
27.0 (t), 30.5 (t), 35.6 (t), 37.1 (d), 42.3 (d), 42.5 (t), 49.1 (d),
52.1 (s), 55.5 (q), 63.1 (d), 95.2 (d), 111.0 (t), 112.3 (d),
113.0 (d), 126.6 (s), 127.8 (2d), 127.9 (d), 129.0 (2d), 129.9
(d), 136.1 (s), 145.8 (s), 147.5 (s), 156.4 (s), 163.2 (s), 197.3
(s), 216.0 (s). HRMS: MC, found 486.2773. C32H38O4
requires 486.2770. MS m/e (%) 486 (MC, 2), 457 (1), 440
(1), 326 (4), 176 (100), 161 (26), 150 (10), 105 (8).
3.1.14. 2-[5-Isopropenyl-2-(3-methoxy-allyl)-2-methyl-3-
oxo-cyclohexyl]-6-methoxy-3,4-dihydro-2H-naphthalen-
1-one (31). The reaction was carried out as described for
compound 18. A complex mixture was obtained from which
a 10.5% yield of 31 could be isolated as a slightly yellow oil
and as a mixture of two isomers (2:3), next to minor
amounts of other compounds. IR (CCl4 sol.) cmK1: 2956,
2938, 2869, 2839, 1707, 1678, 1601, 1250; 1H NMR (C6D6)
d: 0.85–3.02 (m, 10H), 0.94 (s, 3H), 1.13 (d, JZ6.7 Hz, 2H),
1.45 (m) and 1.63 (M) (s, 3H), 3.23 (s, 3H), 3.26 (s, 3H),
3.38–3.54 (m, 1H), 4.75 (dt, J1Z7.8 Hz, J2Z12.6 Hz, 1H),
4.86 (s, 1H), 4.89 (M) and 4.94 (m) (s, 1H), 6.35 (d, JZ
12.6 Hz, 1H), 6.40–6.69 (m, 3H), 8.25 (d, JZ8.6 Hz, 1H);
13C NMR (C6D6) d: 13.0 (M) and 21.8 (m) (q), 20.8 (M) and
20.9 (m) (q), 26.5 (M) and 26.7 (m) (t), 27.0 (M) and 29.4
(m) (t), 29.4 (m) and 30.1 (M) (t), 35.1 (M) and 40.5 (m) (d),
35.6 (t), 41.6 (M) and 47.8 (m) (d), 42.5 (M) and 44.0 (m) (t),
48.4 (m) and 48.7 (M) (d), 51.8 (s), 54.6 (q), 55.1 (q), 97.1
(d), 111.4 (M) and 112.6 (m) (t), 112.7 (2d), 129.8 (m) and
130.1 (M) (d), 130.1 (s), 145.7 (s), 146.5 (s), 147.1 (s), 149.7
(d), 163.3 (s), 196.0 (M) and 196.8 (m) (s), 210.4 (m) and
213.1 (M) (s). HRMS: MC, found 396.2307. C25H32O4
requires 396.2301. MS m/e (%) 396 (MC, 2), 364 (2), 326
(6), 325 (5), 176 (100), 161 (6), 150 (15), 71 (13).
Mixture of isomers 27c and 27d. 1H NMR (CDCl3) d: 0.77–
3.30 (m), 1.05 (M) and 1.32 (m) (t, JZ7.1 Hz, 3H), 1.17
(m) and 1.21 (M) (s, 3H), 1.61 (m) and 1.76 (M) (s, 3H), 3.56
(M, dq, J1Z5.3 Hz, J2Z7.1 Hz) and (3.79 (m, q, JZ7.1 Hz)
(2H), 3.83 (s, 3H), 4.50 (m, dd, J1Z5.7 Hz, J2Z9.3 Hz) and
5.00 (M, t, JZ8.7 Hz) (1H), 4.61 (m) and 4.72 (M) (s, 1H),
4.80 (br s, 1H), 6.60 (m) and 6.66 (M) (d, JZ2.6 Hz, 1H),
6.80 (dd, JZ2.6, 8.7 Hz, 1H), 7.03–7.65 (m, 5H), 7.97 (M)
and 7.99 (m) (d, JZ8.7 Hz, 1H); 13C NMR (CDCl3) d: 14.8
(m) and 15.4 (M) (q), 20.4 (M) and 20.7 (m) (q), 20.8 (q),
27.1 (t), 27.4 (t), 30.7 (t), 34.4 (M) and 35.4 (m) (t), 37.2
(m) and 38.8 (M) (d), 42.2 (m) and 42.5 (M) (d), 42.6 (t),
49.1 (m) and 49.7 (M) (d), 51.4 (M) and 52.0 (m) (s), 55.5
(q), 63.1 (m) and 65.6 (M) (t), 108.8 (d), 110.8 (t), 112.3 (d),
113.1 (d), 126.5 (s), 126.6 (d), 127.9 (d), 128.2 (2d), 128.9
(d), 130.0 (d), 136.2 (s), 145.9 (s), 147.5 (s), 155.7 (s), 163.3
(s), 197.5 (s), 216.3 (s).
3.1.15. 3-Isopropenyl-1,8-dimethoxy-14a-methyl-12-
phenyl-1,2,3,4,4a,4b,5,6,10b,14,14a-undecahydro-11-
oxa-benzo[3,4]cycloocta[1,2-a]naphthalene (33). The
reaction was carried out as described for compound 29.
The acetal 33 was obtained as a slightly yellow oil in 37%
yield. IR (CCl4 sol.) cmK1: 2937, 2833, 1649, 1607, 1496,
1449, 1252, 1039; 1H NMR (C6D6) d: 0.93 (s, 3H), 1.70 (s,
3H), 1.34–2.62 (m, 12H), 3.10–3.35 (m, 1H), 3.24 (s, 3H),
3.40 (s, 3H), 3.46 (s, 3H), 3.92 (dd, J1Z3.9 Hz, J2Z
11.7 Hz, 1H), 5.03 (s, 1H), 5.08 (s, 1H), 5.24 (dt, J1Z
7.8 Hz, J2Z12.7 Hz, 1H), 6.31 (d, JZ12.6 Hz, 1H), 6.69
(dd, J1Z2.5 Hz, J2Z8.4 Hz, 1H), 6.77 (d, JZ2.5 Hz, 1H),
7.33 (d, JZ8.4 Hz, 1H); 13C NMR (C6D6) d: 13.8 (q), 22.7
(q), 25.1 (t), 29.2 (t), 29.4 (t), 32.5 (t), 36.5 (d), 37.8 (t), 39.0
(d), 43.5 (s), 54.6 (q), 55.2 (q), 58.7 (q), 70.8 (d), 100.1 (d),
110.7 (t), 111.1 (d), 113.6 (d), 123.7 (d), 124.3 (s), 124.6 (s),
139.3 (s), 147.1 (s), 148.4 (d), 149.6 (s), 159.0 (s). HRMS:
MC, found 412.2612. C26H36O4 requires 412.2614. MS m/e
(%) 412 (MC, 100), 380 (17), 269 (40), 216 (48), 203 (64),
190 (64), 75 (33), 71 (25).
3.1.13. 3-Isopropenyl-1,8, 10b-trimethoxy-14a-methyl-
1,2,3,4,4a,4b,5,6,10b,14,14a-undecahydro-11-oxa-benzo-
[3,4]cycloocta[1,2-a]naphthalene (29). Compound 27b
(100 mg, 0.21 mmol) was dissolved in THF (7 ml) and
Li(tBuO)3AlH (104 mg, 0.42 mmol) was added in two
portions (second portion after 1 h reaction time). The
reaction mixture was refluxed during 3 h and then the
solution was cooled on ice, treated with EtOAc (2 ml), 1 M
NaHSO4 solution (0.5 ml) and filtered over a short plug of
Na2SO4. The solvent was evaporated and the residue was
dissolved in DMSO (2 ml) and cooled on ice before
pulverised KOH (47 mg, 0.84 mmol) was added. After
stirring for 5 min, MeI (26 ml, 0.42 mmol) was added and
stirring was continued for 2 h at room temperature. The
reaction mixture was diluted with CH2Cl2 (10 ml) and
washed with water (10 ml) and brine (10 ml), dried
(MgSO4) and solvent removed under reduced pressure.
Column chromatography (PE/EtOAc 3:1) afforded