N. Fujiwara et al. / Tetrahedron: Asymmetry 17 (2006) 3037–3045
3041
10.67. Found: C, 77.34; H, 10.82. FAB MS m/z: 265
luted with brine and extracted with Et2O. The organic layer
was then dried over MgSO4. Evaporation of the organic
solvent gave a crude product, which was chromatographed
on silica gel (15 g, n-hexane–AcOEt = 10:1) to afford (ꢀ)-
(M++1).
6.5. (1R,2R,4aS,8aS)-(ꢀ)-1,2,3,4,4a,5,6,7,8,8a-Decahydro-
2-hydroxy-2,5,5,8a-tetramethyl-1-naphthalene-propanol 10
12 (0.419 g, 88%) as a colorless oil. Compound (ꢀ)-12;
24
½aꢁD ¼ ꢀ17:3 (c 0.79, CHCl3); IR (neat): 1739, 1242,
1
To a suspension of LiAlH4 (0.162 g, 4.3 mmol) in Et2O
(80 ml) was added a solution of (+)-9 (0.943 g, 3.8 mmol)
in Et2O (35 ml) at 0 °C and the whole mixture was stirred
for 3 h at room temperature. The reaction mixture was di-
luted with 2 M aqueous NaOH and filtered with the aid of
Celite. The filtrate was then extracted with ether. The ether
layer was washed with brine and dried over MgSO4. Evap-
oration of the organic layer gave a residue, which was chro-
matographed on silica gel (20 g, n-hexane–AcOEt = 1:1) to
1144 cmꢀ1; H NMR: d 0.75 (3H, s), 0.79 (3H, s), 0.83
(3H, s), 0.86–0.97 (2H, m), 1.06–1.28 (4H, m), 1.15 (3H,
s), 1.30–1.56 (5H, m), 1.56–1.80 (4H, m), 1.91 (1H, dt,
J = 3.5, 12 Hz), 2.00 (3H, s), 3.31 (3H, s), 3.98 (1H, dt,
J = 7, 13 Hz), 4.03 (1H, dt, J = 7, 13 Hz), 4.60 (1H, d,
J = 7.5 Hz), 4.72 (1H, d, J = 7.5 Hz). 13C NMR: d 15.8
(q), 18.5 (q), 20.1 (t), 20.7 (q), 21.2 (q), 21.6 (q), 22.1 (t),
31.8 (t), 33.3 (s), 33.4 (q), 39.2 (s), 39.8 (t), 40.0 (t), 40.2
(t), 42.0 (t), 55.0 (q), 56.0 (d), 59.5 (d), 65.2 (t), 80.0 (s),
89.6 (t), 170.9 (s). Anal. Calcd for C21H38O4: C, 71.15;
H, 11.04. Found: C, 71.66; H, 10.93.
give (ꢀ)-10 (0.464 g, 48%). Compound (ꢀ)-10: mp 133–
27
133.5 °C (colorless needles from AcOEt); ½aꢁD ¼ ꢀ7:3 (c
0.82, CHCl3); IR (KBr): 3395 cmꢀ1 (OH); NMR: d 0.77
(3H, s), 0.78 (3H, s), 0.85 (3H, s), 0.87–1.00 (2H, m),
1.07–1.17 (1H, m), 1.14 (3H, s), 1.18–1.31 (2H, m), 1.31–
1.46 (4H, m), 1.46–1.63 (5H, m), 1.63–1.74 (1H, m), 1.82
(1H, dt, J = 3, 12 Hz), 1.95 (1H, br s; disappeared with
D2O), 3.60 (1H, dt, J = 5, 10 Hz), 3.70 (1H, ddd, J = 4,
5, 11 Hz). 13C NMR: d 15.4 (q), 18.5 (q), 20.7 (t, t), 21.6
(q), 24.6 (q), 33.3 (s), 33.5 (q), 34.3 (t), 39.2 (s), 39.8 (t),
42.0 (t), 44.3 (t), 56.1 (d), 59.0 (d), 61.8 (t), 74.6 (s). Anal.
Calcd for C17H32O2: C, 76.06; H, 11.92. Found: C, 75.62;
H, 12.03.
6.8. (1R,2R,4aS,8aS)-(ꢀ)-1,2,3,4,4a,5,6,7,8,8a-Decahydro-
2-(methoxymethyloxy)-2,5,5,8a-tetramethyl-1-naphthalene-
propanol 13
A mixture of (ꢀ)-12 (0.403 g, 1.14 mmol) and K2CO3
(0.189 g, 1.37 mmol) in MeOH (10 ml) was stirred for
2.5 h at room temperature. The reaction mixture was di-
luted with brine and extracted with Et2O. The organic layer
was dried over MgSO4. Evaporation of the organic solvent
gave a crude product, which was chromatographed on sil-
ica gel (15 g, n-hexane–AcOEt = 5:1) to afford (ꢀ)-13
6.6. (1R,2R,4aS,8aS)-(ꢀ)-1-(30-Acetoxypropyl)-
1,2,3,4,4a,5,6,7,8,8a-decahydro-2-hydroxy-2,5,5,8a-tetra-
methylnaphthalene 11
(0.349 g, 98%) as a colorless oil. Compound (ꢀ)-13;
25
½aꢁD ¼ ꢀ29:7 (c 0.96, CHCl3); IR (neat): 3413,
1
1143 cmꢀ1; H NMR: d 0.75 (3H, s), 0.81 (3H, s), 0.83
(3H, s), 0.88–1.01 (2H, m), 1.16 (3H, s), 1.11 (1H, dt,
J = 4, 11 Hz), 1.22 (1H, dt, J = 3, 13 Hz), 1.30–1.43 (4H,
m), 1.45–1.74 (7H, m), 1.96 (1H, dt, J = 3, 12 Hz), 3.04
(1H, br s; disappeared with D2O), 3.33 (3H, s), 3.57 (1H,
dt, J = 5, 10 Hz with D2O), 3.67 (1H, ddd, J = 4, 8,
12 Hz with D2O), 4.67 (1H, d, J = 7 Hz), 4.71 (1H, d,
J = 7 Hz). 13C NMR: d 15.7 (q), 18.4 (t), 20.1 (t), 20.2
(q), 21.1 (t), 21.6 (q), 33.2 (s), 33.4 (q), 34.2 (t), 39.3 (s),
40.0 (t), 40.1 (t), 42.0 (t), 55.3 (q), 55.9 (d), 57.9 (d), 62.1
(t), 81.0 (s), 89.7 (t). Anal. Calcd for C19H36O3: C, 73.03;
H, 11.61. Found: C, 72.99; H, 11.67.
A mixture of (ꢀ)-10 (0.415 g, 1.54 mmol), Ac2O (0.199 g,
1.95 mmol) and 4-dimethylaminopyridine (DMAP;
0.019 g, 0.15 mmol) in pyridine (5 ml) was stirred for 3 h
at room temperature. The reaction mixture was diluted with
7% aqueous NaHCO3 and extracted with Et2O. The organic
layer was washed with brine and dried over MgSO4. Evap-
oration of the organic solvent gave a crude product, which
was chromatographed on silica gel (15 g, n-hexane–
AcOEt = 5:1) to afford (ꢀ)-11 (0.456 g, 95%) as a colorless
22
oil. Compound (ꢀ)-11; ½aꢁD ¼ ꢀ1:9 (c 0.87, CHCl3); IR
1
(neat): 3489, 1733, 1248 cmꢀ1; H NMR: d 0.76 (3H, s),
0.84 (3H, s), 0.86–0.95 (2H, m), 1.04 (1H, t, J = 4 Hz),
1.06–1.19 (2H, m), 1.11 (3H, s), 1.21–1.31 (2H, m), 1.31–
1.38 (2H, m), 1.38–1.47 (2H, m), 1.50–1.78 (5H, m), 1.84
(1H, dt, J = 3, 12 Hz), 2.02 (3H, s), 4.02 (1H, dt, J = 7,
14 Hz), 4.04 (1H, dt, J = 7, 14 Hz). 13C NMR: d 15.5 (q),
18.6 (q), 20.7 (t), 21.2 (q), 21.6 (q), 21.7 (t), 24.1 (q), 32.0
(t), 33.3 (s), 33.5 (q), 39.2 (s), 39.8 (t), 42.0 (t), 44.7 (t),
56.1 (d), 61.6 (d), 65.0 (t), 74.1 (s), 170.9 (s). Anal. Calcd
for C19H34O3: C, 73.50; H, 11.04. Found: C, 73.76; H, 11.06.
6.9. (1R,2R,4aS,8aS)-(ꢀ)-1,2,3,4,4a,5,6,7,8,8a-Decahydro-
2-(methoxymethyloxy)-2,5,5,8a-tetramethyl-1-naphthalene-
propanal 14
A mixture of (ꢀ)-13 (0.332 g, 1.06 mmol), Florisil (1.17 g)
and pyridinium dichromate (PDC; 1.17 g, 31 mmol) in
CH2Cl2 (10 ml) was stirred for 3.5 h at 40 °C. The reaction
mixture was filtered with the aid of Celite. The filtrate was
evaporated to give a residue, which was chromatographed
on silica gel (15 g, n-hexane–AcOEt = 10:1) to afford
6.7. (1R,2R,4aS,8aS)-(ꢀ)-1-(30-Acetoxypropyl)-
1,2,3,4,4a,5,6,7,8,8a-decahydro-2-(methoxymethyloxy)-
2,5,5,8a-tetramethylnaphthalene 12
(ꢀ)-14 (0.252 g, 77%) as a colorless oil. Compound
26
(ꢀ)-14; ½aꢁD ¼ ꢀ5:2 (c 0.99, CHCl3); IR (neat): 1724,
1
1143 cmꢀ1; H NMR: d 0.75 (3H, s), 0.80 (3H, s), 0.82
(3H, s), 0.85–0.94 (2H, m), 1.06–1.25 (3H, m), 1.17 (3H,
s), 1.30–1.43 (2H, m), 1.43–1.66 (5H, m), 1.68–1.82 (1H,
m), 1.93 (1H, dt, J = 3, 12 Hz), 2.44 (1H, dddd, J = 2, 8,
9, 17 Hz), 2.56 (1H, dddd, J = 2, 7, 9, 17 Hz), 3.28 (3H,
d, J = 1 Hz), 4.61 (1H, dd, J = 1, 7 Hz), 4.71 (1H, dd,
A mixture of (ꢀ)-11 (0.416 g, 1.34 mmol), chloromethyl-
methyl ether (MOM-Cl; 0.33 g, 4.09 mmol) and N,N-diiso-
propylethylamine (0.359 g, 2.78 mmol) in DMF (5 ml)
was stirred for 1 h at 80 °C. The reaction mixture was di-