1342
Vol. 49, No. 10
as orange crystals (475.1 mg, 75.9%). 9: mp. 151—155 °C (lit.12) 155 °C); Rf
ϭ0.34 (CHCl3 : CH3OHϭ50 : 1). H-NMR (400 MHz, CDCl3) d: 7.32 (2H,
156.5 (s, C-8), 147.3 (s, C-5), 126.6 (d, C-6), (s, C-10), 118.4 (d, C-7), 114.8
(s, C-9), 67.2 (d, C-4), 35.4 (t, C-2), 31.4 (t, C-3). IR (CHCl3) cmϪ1: 1640,
1600. HR-EI-MS m/z: 194.0576 [M]ϩ (Calcd for C10H10O4: 194.0579).
X-Ray Crystallographic Analysis of 1a Compound 1a was crystallized
from AcOEt to give a red prismatic crystal of C10H10O4 having approximate
dimensions of 0.400ϫ0.400ϫ0.300 mm, which was mounted on a glass
fiber.
Crystal Data for 1a: Formula C10H10O4, fwϭ194.19; triclinic, space group
P1(#2), aϭ9.826(3) Å, bϭ12.380(2) Å, cϭ8.648(2)Å, aϭ106.43(2)°, bϭ
111.54(2)°, gϭ68.10(2)°, Vϭ894.9(4)Å3; Zϭ4, Dcalcϭ1.441 g/cm3. Rϭ
0.088, Rwϭ0.096 for 1984 observed reflections with IϾ5.00s(I). All mea-
surements were made on a Rigaku AFC5S diffractometer with graphite
monochromated CuKa radiation (lϭ1.54178Å) and a 12 KW rotating
anode generator. Cell constants and an orientation matrix for date collection
were obtained from a least-squares. The data were collected at a temperature
of 23Ϯ1 °C using the w–2q scan technique to a maximum 2q value of
135.1°, and were corrected for Lorentz and polarization effects. The struc-
ture was solved by direct methods using MITHRIL.21) The non-hydrogen
atoms were refined anisotropically. All calculations were performed using
the TEXSAN22) crystallographic software package of the Molecular Struc-
ture Corporation.
1
s, 6,7-H), 6.77 (2H, s, 2,3-H), 3.95 (6H, s, 5,8-OCH3). 13C-NMR (100.6
MHz, CDCl3) d: 184.8 (s, C-1, 4), 153.7 (s, C-5, 8), 138.3 (d, C-2, 3), 120.4
(d, C-6, 7), 119.7 (s, C-9, 10), 56.9 (q, 5,8-OCH3). IR (CHCl3) cmϪ1: 1640.
HR-FAB-MS m/z: 220.0737 [Mϩ2H]ϩ (Calcd for C12H12O4: 220.0735).
Cis- and trans-5,8-Dimethooxy-1,2,3,4-tetrahydronaphthalene-1,4-diol
(11a, 11b) To a solution of 9 (50.0 mg, 0.23 mmol) in CH3OH (8 ml) were
added CeCl3·7H2O (68.6 mg, 0.18 mmol) and NaBH4 (34.8 mg, 0.92 mmol)
at room temperature. After stirring for 30 min, excess NaBH4 was quenched
by H2O (5 ml). The mixture was evaporated in vacuo and was further added
H2O (5 ml) and extracted with CHCl3 (30 mlϫ3). The CHCl3 layer was
washed with brine (5 mlϫ2), dried over Na2SO4, and concentrated in vacuo
to give the crude products (the mixture of 10a and 10b) (55.0 mg).
A solution of the crude products (the mixture of 10a and 10b) in EtOH (3
ml) was added to a suspension of PtO2 (10 mg) in EtOH (1 ml) and hydro-
genated for 25 min. After the reaction was completed, PtO2 was removed by
filtration. The filtrate was evaporated in vacuo to give the crude compounds
of 11a and 11b (60.9 mg). These compounds were purified by column chro-
matography (hexane : AcOEtϭ2 : 1) to give 11a as orange oil (16.1 mg,
31.3%) and 11b as orange crystals (15.8 mg, 30.8%). 11a: Rfϭ0.21 (ben-
zene : AcOEtϭ1 : 1). 1H-NMR (400 MHz, CDCl3) d: 6.78 (2H, s, 6,7-H),
4.97 (2H, t, Jϭ5.5 Hz, 1,4-H), 3.85 (6H, s, 5,8-OCH3), 3.46 (2H, br, 1,4-
OH), 2.03—2.13, 1.86—1.96 (2H, m, each 2,3-H2). 13C-NMR (100.6 MHz,
CDCl3) d: 151.9 (s, C-5, 8), 128.9 (s, C-9, 10), 109.5 (d, C-6, 7), 64.5 (d, C-
1, 4), 55.8 (q, 5, 8-OCH3), 26.3 (t, C-2, 3). IR (CHCl3) cmϪ1: 3550, 2900,
1600. HR-FAB-MS m/z: 224.1042 [M]ϩ (Calcd for C12H16O4: 224.1049).
11b: mp. 113—114 °C; Rfϭ0.33 (benzene : AcOEtϭ1 : 1). 1H-NMR (400
MHz, CDCl3) d: 6.79 (2H, s, 6, 7-H), 5.02 (2H, t, Jϭ2.0 Hz, 1, 4-H), 3.85
(6H, s, 5,8-OCH3), 2.83 (2H, br, 1,4-OH), 2.12—2.18, 1.86—1.94 (2H, m,
each 2,3-H2). 13C-NMR (100.6 MHz, CDCl3) d: 151.7 (s, C-5, 8), 128.1 (s,
C-9, 10), 109.6 (d, C-6, 7), 62.6 (d, C-1, 4), 55.8 (q, 5,8-OCH3), 24.9 (t, C-2,
3). IR (CHCl3) cmϪ1: 3550, 2900, 1600. HR-FAB-MS m/z: 224.1042 [M]ϩ
(Calcd for C12H16O4: 224.1049).
1a from 11a A solution of CAN (97.6 mg, 0.18 mmol) in CH3CN (2.4
ml) was added dropwise to a solution of 11a (20.3 mg, 0.09mmol) in
CH3CN (1.4 ml) at 0 °C. The mixture was stirred at room temperature for 30
min, and was evaporated in vacuo. Brine (3 ml) was added to the residue,
and was extracted with CHCl3 (20 mlϫ4). The CHCl3 layer was dried over
Na2SO4 and evaporated in vacuo. The residue was purified by preparative
TLC (CHCl3 : CH3OHϭ50 : 1) to give 1a as yellow crystals (11.1 mg,
63.1%). 1a was identical with 1a obtained from 7 described above by com-
parison of the 1H-NMR spectra.
Reference and Notes
1) Chu M., Truumees I., Patel M. G., Gullo V. P., Blood C., King I., Pai
J.-K., Puar M. S., Tetrahedron Lett., 35, 1343—1346 (1994).
2) Sakemi S., Inagaki T., Kaneda K., Hirai H., Iwata E., Sakakibara T.,
Yamauchi Y., Norcia M., Wondrack L. M., Sutcliffe J. A., Kojima N.,
J. Antibiot., 48, 134—142 (1995).
3) Barett A. G. M., Hamprecht D., Meyer T., Chem. Commun., 1998,
809—810.
4) Ragot J. P., Alcaraz M.-L., Taylor R. J. K., Tetrahedron Lett, 39,
4921—4924 (1998).
5) Wipf P., Jung J.-K., J. Org. Chem., 63, 3530—3531 (1998).
6) Wipf P., Jung J.-K., Rodríguez S., Lazo J. S., Tetrahedron, 57, 283—
296 (2001).
7) Chi S., Heachcock C. H., Org. Lett., 1, 3—5 (1999).
8) Wipf P., Jung J.-K., J. Org. Chem., 64, 1092—1093 (1999).
9) Wipf P., Jung J.-K., J. Org. Chem., 65, 6319—6337 (2000).
10) Ragot J. P., Steeneck C., Alcaraz M.-L., Taylor R. J. K., J. Chem. Soc.,
Perkin Trans. 1, 1999, 1073—1082.
11) Ragot J. P., Prime M. E., Archibald S. J., Taylor R. J. K., Org. Lett., 2,
1613—1616 (2000).
12) Pearson M. S., Jensky B. J., Greer F. X., Hagstrom J. P., Wells N. M., J.
Org. Chem., 43, 4617—4622 (1978).
13) Luche J.-L., Rodriguez-Hahn L., Crabbé P., J. Chem. Soc., Chem.
Commun., 1978, 601—602.
14) Gemal A. L., Luche J.-L., J. Am. Chem. Soc., 103, 5454—5459 (1981).
15) Marchand A. P., LaRoe W. D., Sharma G. V. M., Suri S. C., Reddy D.
S., J. Org. Chem., 51, 1622—1625 (1986).
16) Broadhurst M. J., Hassall C. H., Thomas G. J., J. Chem. Soc., Chem.
Commun., 1982, 158—160.
17) Takeuchi Y., Sudani M., Yoshii E., J. Org. Chem., 48, 4151—4152
(1983).
1b from 11b A solution of CAN (142.5 mg, 0.26 mmol) in CH3CN (3.5
ml) was added dropwise to a solution of 11b (29.2 mg, 0.13mmol) in
CH3CN (2.0 ml) at 0 °C. The mixture was stirred at room temperature for 30
min, and was evaporated in vacuo. Brine (3 ml) was added to the residue,
and was extracted with CHCl3 (30 mlϫ3). The CHCl3 layer was dried over
Na2SO4 and evaporated in vacuo. The residue was purified by preparative
TLC (CHCl3 : CH3OHϭ50 : 1) to give 1b as yellow oil (11.4 mg, 45.2%). 1b
was identical with 1b obtained from 7 described above by comparison of the
1H-NMR spectra.
4,5,8-Trihydroxy-1,2,3,4-tetrahydronaphthalene-1-one (3) To a solu-
tion of 7 (200.0 mg, 1.04 mmol) in THF (12 ml) were added CeCl3·7H2O
(155.0 mg, 0.42 mmol) and NaBH4 (39.3 mg, 1.04 mmol) at 0 °C. After stir-
ring for 30 min, the reaction was quenched by H2O (5.0 ml). The mixture
was evaporated in vacuo and the residue was acidified to pH3 with 10%
aqueous HCl and extracted with AcOEt (50 mlϫ2). The AcOEt layer was
dried over Na2SO4 and concentrated in vacuo. The residue was purified by
preparative TLC (CHCl3 : CH3OHϭ10 : 1) to give 3 as yellow oil (155.4 mg,
18) Kawasaki M., Matsuda F., Terashima S., Tetrahedron, 44, 5713—5725
(1988).
19) The NaBH4–CeCl3 reduction of 7 was examined at several tempera-
tures and the ratio of the yields of 1a and 1b from 7 at 80 °C, room
temperature and Ϫ70 °C exhibited 1: 1.5 (82%), 1: 1.5 (84%) and 1: 2
(94%), respectively. (Total yield is described in parenthesis.)
20) The NaBH4–CeCl3 reduction of 9 was examined at several tempera-
tures and the yields of 11a and 11b from 9 at 75 °C and Ϫ50 °C exhib-
ited 26 and 33%, and 27 and 42%, respectively.
21) Gilmore C. J., J. Appl. Cryst., 17, 42—46 (1984).
22) TEXSAN-TEXRAY Structure Analysis Package, Molecular Structure
Corporation, 1985.
1
77.0%). 3: Rfϭ0.41 (CHCl3 : CH3OHϭ10 : 1). H-NMR (400 MHz, CDCl3)
d: 12.02 (1H, s, 8-OH), 7.77 (1H, br, 5-OH), 7.07 (1H, d, Jϭ9.0 Hz, 6-H),
6.85 (1H, d, Jϭ9.0 Hz, 7-H), 5.27 (1H, dd, Jϭ5.5, 10.0 Hz, 4-H), 2.78—
2.90, 2.56—2.70 (1H, m, each 2-H), 2.37—2.48, 2.11—2.26 (1H, m, each
3-H), 1.70 (1H, br, 4-OH). 13C-NMR (100.6 MHz, CDCl3) d: 203.4 (s, C-1),