1752
N. MORI et al.
Experimental
OCH3), 4.21 (2H, dd, J ¼ 4:2, 9.9 Hz, CHaOMs), 4.32
(2H, dd, J ¼ 5:7, 9.9 Hz, CHbOMs), 6.38 (4H, s, ArH).
13C-NMR ꢁ (CDCl3) ppm: 34.5, 37.4, 40.1, 56.1, 60.8,
69.1, 105.9, 134.2, 136.7, 153.4. Anal. Calcd. for
C26H38O12S2: C, 51.47; H, 6.31. Found: C, 51.34; H,
6.34.
Optical rotation values were recorded with a Jasco
DIP-1000 polarimeter. IR spectra were measured with
a Jasco FT/IR-230 spectrophotometer. 1H-NMR (300
MHz) and 13C-NMR (75 MHz) data were recorded with
a Jeol JNM AL300 instrument. Chemical shifts (ꢁ) are
referenced to the residual solvent peak as the internal
standard (CDCl3: ꢁH ¼ 7:26, ꢁC ¼ 77:0). Mass spectra
were recorded with a Jeol JMS-700T instrument.
Column chromatography was performed with Merck
silica gel 60 (0.060–0.200 mm). Melting point values are
uncorrected.
(2R,3R)-2,3-Dimethyl-1,4-bis(3,4,5-trimethoxyphen-
yl)butane (7). To a solution of 6 (74.8 mg, 0.123 mmol)
in THF (6 ml) was added LAH (20 mg, 0.527 mmol) at
0 ꢀC, and the mixture was refluxed for 2 h. After cooling
to 0 ꢀC, water and 3 N HCl were added, and the reaction
mixture was extracted with CHCl3. The organic layer
was dried with anhydrous magnesium sulfate and
concentrated in vacuo. The residue was chromatograph-
ed over silica gel. Elution with hexane/ethyl acetate
(3:1) gave 7 (47.5 mg, 92%). Recrystallization from
(R)-MTPA ester of racemic 5. To a solution of
racemic 5 (1 mg) in pyridine (2 drops) was added (S)-
MTPACl (1 drop). After stirring overnight, the reaction
mixture was diluted with ethyl acetate, and successively
washed with a diluted HCl solution, saturated NaHCO3
solution, water and brine. The organic layer was dried
with anhydrous magnesium sulfate and concentrated in
vacuo. 1H-NMR ꢁ (CDCl3) ppm: 1.97–2.79 (6H, m),
3.50 (6H, s), 3.72 (12/2H, s), 3.74 (12/2H, s), 3.81 (6/
2H, s), 3.82 (6/2H, s), 4.01 (2/2H, dd, J ¼ 5:7, 11.4
Hz), 4.16 (2/2H, dd, J ¼ 4:8, 11.4 Hz), 4.37 (2/2H, dd,
J ¼ 4:5, 11.4 Hz), 4.49 (2/2H, dd, J ¼ 4:8, 11.4 Hz),
6.16 (4/2H, s), 6.21 (4/2H, s), 7.35–7.48 (10H, m).
MeOH gave colorless needles.
22
Mp 116–118 ꢀC. ½ꢀꢂ
ꢁ33 (c 0.5, CHCl3). IR ꢂmax
D
(KBr) cmꢁ1: 2930, 1585, 1509, 1467, 1421, 1325, 1240,
1
1134, 997. H-NMR ꢁ (CDCl3) ppm: 0.86 (6H, d, J ¼
6:6 Hz, 2-CH3 and 3-CH3), 1.77 (2H, m, 2-H and 3-H),
2.42 (2H, dd, J ¼ 7:5, 13.5 Hz, 1-Ha and 4-Ha), 2.54
(2H, dd, J ¼ 7:5, 13.5 Hz, 1-Hb and 4-Hb), 3.80 (12H, s,
OCH3), 3.82 (6H, s, OCH3), 6.28 (4H, s, ArH). 13C-
NMR ꢁ (CDCl3) ppm: 13.8, 37.2, 41.7, 56.0, 60.8,
105.7, 135.9, 137.3, 152.9. Anal. Calcd. for C24H34O6:
C, 68.87; H, 8.19. Found: C, 69.36; H, 8.23.
(R)-MTPA ester of 5. To a solution of recrystallized
5 (1 mg) in pyridine (2 drops) was added (S)-MTPACl
(1 drop). After stirring for 2 days, the reaction mixture
was diluted with ethyl acetate, and successively washed
with a diluted HCl solution, saturated NaHCO3 solution,
water and brine. The organic layer was dried with an-
hydrous magnesium sulfate and concentrated in vacuo.
1H-NMR ꢁ (CDCl3) ppm: 2.01–2.13 (2H, m), 2.42–2.62
(4H, m), 3.50 (6H, s), 3.74 (12H, s), 3.81 (6H, s), 4.01
(2H, dd, J ¼ 5:7, 11.4 Hz), 4.49 (2H, dd, J ¼ 4:8, 11.4
Hz), 6.16 (4H, s), 7.35–7.48 (10H, m). Other peaks
corresponding to the diastereomer were not observed.
Sauriol A (1). To a solution of 7 (47.5 mg, 0.113
mmol) in CH2Cl2 (3 ml) was added BBr3 (1.0 M in
CH2Cl2, 1.0 ml, 1.0 mmol) at 0 ꢀC. After stirring for
5 min, the reaction mixture was poured into water and
extracted with CHCl3. The organic layer was dried with
anhydrous sodium sulfate and concentrated in vacuo.
The residue was chromatographed over silica gel.
Elution with hexane/ethyl acetate (2:1) gave 1 (32.1
mg, 78%) as an amorphous solid.
22
½ꢀꢂ
ꢁ23 (c 0.94, CHCl3), lit. ½ꢀꢂD ꢁ240 (c 0.03,
D
CHCl3). IR ꢂmax (CHCl3) cmꢁ1: 3556, 3022, 2962,
1
1618, 1518, 1466, 1304, 1238, 1201, 1097. H-NMR ꢁ
(2R,3R)-2,3-Bis(methanesulfonyloxymethyl)-1,4-bis(3,
4,5-trimethoxyphenyl)butane (6). To a solution of 56)
(58.9 mg, 0.131 mmol) and triethylamine (50 ml, 0.359
mmol) in CH2Cl2 (2 ml) was added MsCl (40 ml, 0.524
mmol) at 0 ꢀC. After stirring for 2 h, the reaction mixture
was poured into water and extracted with CHCl3. The
organic layer was dried with anhydrous magnesium
sulfate and concentrated in vacuo. The residue was
chromatographed over silica gel. Elution with hexane/
ethyl acetate (1:3) gave 6 (74.8 mg, 94%). Recrystalli-
(CDCl3) ppm: 0.81 (6H, d, J ¼ 6:6 Hz, 9-H and 90-H),
1.74 (2H, m, 8-H and 80-H), 2.35 (2H, dd, J ¼ 7:5,
13.5 Hz, 7-Ha and 70-Ha), 2.49 (2H, dd, J ¼ 7:2, 13.5
Hz, 7-Hb and 70-Hb), 3.81 (6H, s, OCH3), 5.25 (2H, br s,
ArOH), 5.29 (2H, br s, ArOH), 6.17 (2H, d, J ¼ 1:5 Hz,
ArH), 6.35 (2H, d, J ¼ 1:5 Hz, ArH). 13C-NMR ꢁ
(CDCl3) ppm: 13.8, 37.1, 41.2, 56.0, 103.8, 109.2,
130.3, 133.5, 143.4, 146.7. FAB-HRMS m=z: calcd. for
C20H27O6 ½M þ Hꢂþ, 363.1808; found, 163.1840.
zation from CH2Cl2/hexane gave colorless crystals.
25
Sauriol B (2). To a solution of 7 (30.0 mg, 0.072
mmol) in CH2Cl2 (1.5 ml) was added BBr3 (1.0 M in
CH2Cl2, 0.65 ml, 0.65 mmol) at ꢁ78 ꢀC. After stirring
overnight, the reaction mixture was poured into water
and extracted with CHCl3. The organic layer was dried
with anhydrous sodium sulfate and concentrated in
vacuo. The residue was chromatographed over silica gel.
Mp 162–165 ꢀC. ½ꢀꢂ
ꢁ15 (c 0.85, CHCl3). IR ꢂmax
D
(KBr) cmꢁ1: 2937, 2828, 1591, 1508, 1466, 1425, 1350,
1241, 1172, 1129, 959. 1H-NMR ꢁ (CDCl3) ppm: 2.27–
2.33 (2H, m, 2-H and 3-H), 2.59 (2H, dd, J ¼ 9:0, 13.8
Hz, 1-Ha and 4-Ha), 2.85 (2H, dd, J ¼ 5:7, 13.8 Hz, 1-
Hb and 4-Hb), 3.01 (6H, s, SO2CH3), 3.83 (18H, s,