BULLETIN OF THE
Note
KOREAN CHEMICAL SOCIETY
vacuo. The residue was purified by silica gel chromatogra-
phy (4:1 hexane–CH2Cl2) to afford 5 (4.54 g, 77%) as color-
less oil. 1H NMR (CDCl3, 400 MHz) δ 7.10 (d, 2H,
J = 11.6 Hz), 6.80 (d, 2H, J = 11.6 Hz), 5.18 (d, 1H,
J = 7.2 Hz), 5.10 (d, 1H, J = 8.0 Hz), 3.80 (s, 3H), 2.59 (t,
2H, J = 8.0 Hz), 2.28 (q, 2H, J = 8.0 Hz), 2.06 (t, 2H,
J = 7.6 Hz), 1.98 (t, 2H, J = 8.0 Hz), 1.69 (s, 3H), 1.61 (s,
3H), 1.56 (s, 3H). 13C NMR (CDCl3, 100 MHz) δ 157.8,
135.8, 131.7, 131.2, 129.5, 124.5, 123.8, 113.8, 55.4, 39.9,
35.3, 30.3, 26.9, 25.8, 17.8, 16.1. HR-MS (EI) calcd. For
C18H26O [M]+ 258.1984; found 258.1985.
was added to a solution of 8 (1.11 g, 3.66 mmol) in THF
(20 mL) at 0 C and the reaction mixture was stirred for
ꢀ
30 min. After the reaction, the reaction mixture was poured
into saturated NH4Cl and extracted with EtOAc. The
organic layer was washed with brine, dried over anhydr.
MgSO4, and concentrated in vacuo. The residue was puri-
fied by silica gel column chromatography (6:1 hexane–
1
EtOAc) to afford 9 (1.06 g, 91%) as a colorless oil. H
NMR (CDCl3, 400 MHz) δ 6.94 (s, 1H), 6.87 (s, 1H), 3.90
(s, 3H), 2.86–2.81 (m, 2H), 2.12 (s, 1H), 1.87 (d, 1H,
J = 7.2 Hz), 1.76–1.20 (m, 7H), 1.60 (s, 3H), 1.58 (s, 3H),
1.87 (d, 1H, J = 7.2 Hz), 1.23 (s, 3H), 0.96 (s, 3H), 0.93
(s, 3H). 13C NMR (CDCl3, 100 MHz) δ 155.1, 149.8,
133.0, 127.3, 126.3, 107.4, 72.4, 50.5, 55.4, 41.8, 39.0,
38.0, 33.6, 33.4, 30.0, 29.9, 24.9, 21.7, 19.2. HR-MS
(EI) calcd. For C21H32O2 [M]+ 316.2402; found 316.2398.
6-Methoxy-1,1,4a-trimethyl-1,2,3,4,4a,9,10,10a-octa-
hydr-ophenanthrene (6). A mixture of RuCl3ÁxH2O
(11.0 mg, 0.05 mmol) and AgOTf (27.0 mg, 0.11 mmol) in
ClCH2CH2Cl (10 mL) was stirred vigorously for 30 min.
Then the compound 5 (1.38 g, 5.34 mmol) in ClCH2CH2Cl
(10 mL) was added at rꢀoom temperature. The resulting
solution was heated to 60 C and stirred for 4 h. TLC anal-
ysis indicated that the reaction was completed, and the
crude was filtered through a short pad silica with the aid of
CH2Cl2. The filterate was concentrated in vacuo and puri-
fied by silica gel chromatography (2:1 hexane–CH2Cl2) to
Ferruginol methyl ether (10). 10% Pd/C (ca.76 mg) was
added to a solution of compound 9 (0.76 g, 2.4 mmol) in
methanol (10 mL)ꢀand acetic acid (10 mL), and the mixture
was stirred at 50 C for 3 h under H2. After the reaction,
the mixture was filtered through celite which was washed
with EtOAc, and the filtrate was concentrated in vacuo.
The residue was purified by silica gel column chromatogra-
phy (10:1 hexane–EtOAc) to afford 10 (0.68 g, 95%) as a
1
afford 6 (1.05 g, 76%) as colorless oil. H NMR (CDCl3,
400 MHz) δ 6.99 (d, 1H, J = 8.4 Hz), 6.85 (s, 1H), 6.69
(dd, 1H, J = 2.8 and 8.4 Hz), 3.80 (s, 3H), 2.91–2.82 (m,
2H), 2.28 (d, 1H, J = 12.8 Hz), 1.88 (d, 1H, J = 7.6 Hz),
1.89–1.72 (m, 3H), 1.53 (d, 1H, J = 1.2 Hz), 1.44 (d, 1H,
J = 3.6 Hz), 1.36 (dd, 1H, J = 2.4 and 12.6 Hz), 1.29 (dt,
1H, J = 2.8 and 4.0 Hz), 1.23 (s, 3H), 0.99 (s, 3H), 0.97 (s,
3H). 13C NMR (CDCl3, 100 MHz) δ 157.8, 151.6, 129.9,
127.6, 110.8, 110.3, 55.4, 50.4, 41.8, 39.0, 38.1, 33.5,
29.7, 24.9, 21.8, 19.4, 19.3. HR-MS (EI) calcd. For
C18H26O [M]+ 258.1984; found 258.1982.
1
colorless oil. H NMR (CDCl3, 400 MHz) δ 6.9 (s, 1H),
6.77 (s, 1H), 3.83 (s, 3H), 3.27 (t, 1H, J = 6.8 Hz),
2.90–2.83 (m, 2H), 1.94–1.38 (m, 9H), 1.25 (s, 3H), 1.24
(s, 3H), 1.22 (s, 3H), 0.99 (s, 3H), 0.96 (s, 3H). 13C NMR
(CDCl3, 100 MHz) δ 155.1, 148.2, 134.3, 127.0, 126.5,
106.7, 55.7, 50.6, 41.9, 39.1, 38.0, 33.6, 33.5, 30.0, 26.6,
25.0, 23.1, 21.8, 19.5. HR-MS (EI) calcd. For C21H32O
[M]+ 300.2453; found 300.2455.
Sugiol methyl ether (3). A solution of CrO3 (0.27 g,
2.70 mmol) in AcOH (15 mL) and H2O (0.3 mL) was added
to a solution of 10 (0.65 g, 2.16 mmol) in AcOH (15 mL),
and the mixture was stirred for 1 h at room temperature. After
the reaction, the mixture was poured into ice water. The aque-
ous solution was neutralized with 1.0 M NaOH solution and
extracted with EtOAc. The organic layer was successively
washed with saturated NaHCO3 solution, brine, dried over
anhyd. MgSO4, and concentrated in vacuo. The residue was
purified by silica gel column chromatography (1:2 hexane–
CH2Cl2) to afford 3 (0.65 g, 95%) as white solids. 1H NMR
(CDCl3, 400 MHz) δ 7.87 (s, 1H), 6.74 (s, 1H), 3.87 (s, 3H),
3.22 (t, 1H, J = 6.8 Hz), 2.69–2.53 (m, 2H), 1.85 (dd, 1H,
J = 4.4 and 13.6 Hz), 1.76 (tt, 1H, J = 3.2 and 13.6 Hz),
1.69–1.50 (m, 3H), 1.27 (d, 1H, J = 4.5 Hz), 1.23 (s, 3H),
1.19 (t, 3H, J = 2.8 Hz), 1.17 (s, 3H), 0.98 (s, 3H), 0.91 (s,
3H). 13C NMR (CDCl3, 100 MHz) δ 198.5, 161.7, 156.4,
135.2, 125.6, 124.1, 104.5, 55.4, 49.7, 41.4, 38.3, 38.0, 36.1,
33.3, 32.6, 26.5, 23.2, 22.4, 21.4, 18.9. HR-MS (EI) calcd.
For C21H30O2 [M]+ 314.2246; found 314.2247.
1-(3-Methoxy-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahy-
drophenanthren-2-yl)ethanone (8). Aluminum chloride
(1.08 g, 8.1 mmol) and acetyl chloride (0.58 mL, 8.1 mmol)
were adꢀded to a solution of 6 (1.05 g, 4.1 mmol) in CH2Cl2
at −10 C, and the reaction mixture was stirred for 1 h at
ꢀ
−5 C. After the reaction, the reaction mixture was poured
into ice water and extracted with EtOAc. The organic layer
was successively washed with saturated NaHCO3 solution,
brine, dried over MgSO4, and concentrated in vacuo. The
residue was purified by silica gel column chromatography
(6:1 hexane–EtOAc) to afford 8 (1.11 g, 90%) as a color-
1
less oil. H NMR (CDCl3, 400 MHz) δ 7.45 (s, 1H), 6.83
(s, 1H), 3.87 (s, 3H), 2.90 (dd, 1H, J = 6.4 and 17.2 Hz),
2.80 (dd, 1H, J = 7.6 and 11.2 Hz), 2.58 (s, 3H), 1.88 (t,
1H, J = 11.6 Hz), 1.91–1.18 (m, 11H), 0.95 (s, 3H), 0.93
(s, 3H). 13C NMR (CDCl3, 100 MHz) δ 199.6, 157.4,
156.5, 131.0, 127.7, 125.6, 107.6, 55.6, 50.1, 41.6, 38.9,
38.6, 33.4, 31.9, 29.3, 21.8, 19.3, 19.1. HR-MS (EI) calcd.
For C20H28O2 [M]+ 300.2089; found 300.2086.
2-(3-Methoxy-4b,8,8-trimethyl-4b,5,6,7,8,8a,9,10-octahy-
drophenanthren-2-yl)propan-2-ol (9). Methyl magne-
sium bromide (3.0 M in diethyl ether, 1.8 mL, 5.49 mmol)
Ferruginol (1). To a solution of 10 (0.2 g, 0.67 mmol) in
CH2Cl2 (6.7 mL) was added BBr3 (1.0 M in CH2Cl2,
2.0 mL, 2.01 mmol) dropwise at 0 ꢀC, and stirring was
Bull. Korean Chem. Soc. 2018, Vol. 39, 1015–1018
© 2018 Korean Chemical Society, Seoul & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim