458
T. Matsumura et al. / Phytochemistry 61 (2002) 455–459
b-d-glucopyranoside (5), phenethyl b-d-glucopyrano-
side (6), 3-methyl b-d-glucopyranoside (7), uridine
detector, solv.; MeCN–H O (17:3), 2 ml/min; t 4.50
2 R
min (same location as that of d-glucose)] showed the
presence of d-glucose. Compound 2a was identified as
junipediol by comparison with published NMR spectral
data (Comte et al., 1997).
(
8), glycerol 2-O-a-l-fucopyranoside (9), meso-ery-
thritol (10), d-threitol (11), 1-deoxy-d-ribitol (12),
3R)-hydroxymethylbutane-1,2,3,4-tetrol (13), 1-deoxy-
(
d-glucitol (15), d-glucitol (16), meso-galactitol (17),
d-mannitol (18) and d-fructose (19).
3.6. l-Fucitol (14)
0
21
ꢀ
3
.3. 2-Methoxy-2-(4 -hydroxyphenyl)ethanol (1)
Amorphous powder, ½ꢀD À5 (c=0.1, H O). Positive
2
+
FAB–MS (without matrix) m/z: 333 [2M+H] ,
+
Amorphous powder, ½ꢀ À15ꢀ (c=0.2, MeOH).
2
1
167.0937 [M+H] (base, calcd for C H O ; 167.0919).
6
D
15
5
Positive FAB–MS m/z: 207 [M+K]+, 191.0675
1
H NMR (Pyridine-d , 500 MHz) ꢁ: 1.60 (3H, d, J=6.5
5
Hz, H -1), 4.26 (1H, br d, J=8.0 Hz, H-3), 4.36, 4.38
3
+
[
[
M+Na] (base, calcd for C H NaO ; 191.0683), 169
9
12
3
+
1
M+H] . H-NMR (Pyridine-d , 500 MHz) ꢁ: 3.34
5
(each 1H, dd, J=6.0, 8.0 Hz, H -6), 4.59 (1H, br d,
2
(
3H, s, 2-OCH ), 3.99 (1H, dd, J=4.0, 11.5 Hz, H-1a),
3
J=8.0 Hz, H-4), 4.77 (1H, br q, J=6.5 Hz, H-2), 4.85
4
J=4.0, 7.5 Hz, H-2), 7.22 (2H, d, J=8.0 Hz, H-3 and
H-5 ), 7.44 (2H, d, J=8.0 Hz, H-2 and H-6 ). 13C-
.16 (1H, dd, J=7.5, 11.5 Hz, H-1b), 4.53 (1H, dd,
0
(1H, br t, J=6.0 Hz, H-5). 13C NMR (Pyridine-d , 125
MHz) ꢁ: 20.76 (C-1), 65.17 (C-6), 67.35 (C-2), 72.15 (C-
4), 72.40 (C-5), 74.97 (C-3).
5
0
0
0
NMR (Pyridine-d , 125 MHz) ꢁ: 56.66 (2-OCH ), 67.68
5
3
0
0
0
(
C-1), 85.94 (C-2), 116.24 (C-3 , C-5 ), 129.05 (C-2 , C-
0
3.7. NaBH reduction of l-fucose
4
6
H-1b/C-2, C-1 ; H-2/C-1 , C-2 , C-6 ; 2-OCH /C-2; H-
), 130.88 (C-1), 158.74 (C-47). HMBC correlations:
0
0
0
0
0
l-Fucose (13 mg, Kanto Chemical Co.) was dissolved
in MeOH (7.5 ml) and stirred with NaBH (10 mg) for 5
3
0
0
0
0
0
0
0
0
0
0
2
C-6 .
,6 /C-1 , C-3 , C-4 , C-5 , C-2; H-3 ,5 /C-1 , C-2 , C-4 ,
4
0
h at room temp, respectively. After the reaction mixture
was condensed in vacuo, it was subjected to silica gel
[CHCl –MeOH (1:1)] and Sephadex LH-20 (MeOH)
3
.4. Junipediol A 4-O-ꢂ-d-glucopyranoside (2)
3
2
1
ꢀ
CC to give l-fucitol [14a; ½ꢀ À4 (c=1.0, H O)]. The
D
H and C NMR spectroscopic data, and optical rota-
2
Amorphous powder, ½ꢀ À34ꢀ (c=0.8, MeOH).
2
5
1
13
D
Positive FAB-MS m/z: 399 [M+K] , 383.1317
+
tion value of 14 were identical with those of 14a.
+
[
[
M+Na] (base, Calcd for C H NaO ; 383.1318), 361
9 12 3
M+H] , 181 [M-C H O +H] . H NMR (Pyridine-
6
d , 500 MHz) d: 3.45 (1H, quint, J=6.0 Hz, H-2 ), 3.70
+
+ 1
12
6
0
5
Acknowledgements
(
Hz, H -1 , H -3 ), 5.62 (1H, d, J=7.5, Glc H-1), 7.05
3H, s, 3-OCH ), 4.30, 4.42 (each 2H, dd, J=6.0, 10.5
0
3
0
The authors thank Mr. Y. Takase and Dr. H. Suzuki
of the Analytical Center of this University for NMR
and MS measurements.
2
2
(
1H, dd, J=2.0, 8.5 Hz, H-6), 7.22 (1H, d, J=8.5 Hz,
H-2), 7.53 (1H, d, J=8.5 Hz, H-5). 13C NMR (Pyridine-
0
d , 125 MHz) d: 51.70 (C-2 ), 55.94 (3-OCH ), 64.70 (C-
1
(
(
5
0
3
0
, C-3 ), 113.85 (C-2), 116.23 (C-5), 121.24 (C-6), 136.89
C-4), 146.57 (C-5), 150.10 (C-6), Glc [62.30 (C-6), 71.23
References
C-4), 74.86 (C-2), 78.39 (C-3), 78.69 (C-5)]. HMBC
0
correlations: H-2/C-3, C-4, C-6, C-2 ; H-5/C-1, C-3,
0
0
0
0
0
Comte, G., Allais, D.P., Chulia, A.J., Vercauterent, J., Pinaud, N.,
1997. Three phenylpropanoids from Juniperus phoenicea. Phy-
tochemistry 44, 1169–1173.
C-4; H-6/C-2. C-4, C-5, C-2 ; H-1 ,3 /C-1, C-2 ; H-2 /C-
0
0
1
, C-2, C-6, C-1 ,3 ; 3-OCH /C-3; Glc H-1/C-4.
3
Kitajima, J., Ishikawa, T., Tanaka, Y., Ono, M., Ito, Y.,
Nohara, T., 1998. Water-soluble constituents of fennel. V. gly-
cosides of aromatic compounds. Chem. Pharm. Bull. 46, 1587–
3
.5. Enzymatic hydrolysis of 2
1
590.
A mixture of 2 (11 mg) and hesperidinase (5 mg, ICN
Biomedicals Inc., Lot. 72635) in water (5 ml) was sha-
ken in a water bath at 37 C for 20 days. The mixture
Kitajima, J., Ishikawa, T., Tanaka, Y., 1998. Water-soluble con-
stituents of fennel. I. Alkyl glycosides. Chem. Pharm. Bull. 46,
ꢀ
1
643–1646.
was evaporated in vacuo to dryness and the residue was
subjected to silica gel chromatography [eluted with
CHCl -MeOH-H O (4:1:0.1 and 1:1:0.1)] to afford 2a (3
mg) and a sugar fraction. The sugar fraction was passed
through Sephadex LH-20 (MeOH) to give a syrup, and
HPLC [carbohydrate analysis (waters), detector;
JASCO RI-930 detector and JASCO OR-990 chiral
Kitajima, J., Suzuki, N., Ishikawa, T., Tanaka, Y., 1998. New hemi-
terpenoid pentol and monoterpenoid glycoside of Torillis japonica
fruit. Chem. Pharm. Bull. 46, 1583–1586.
3
2
Kitajima, J., Ishikawa, T., Tanaka, Y., Ida, Y., 1999. Water-soluble
constituents of fennel. IX. Glucides and nucleosides. Chem. Pharm.
Bull. 47, 988–992.
Kitajima, J., Ishikawa, T., Aoki, Y., 2001. Glucides of Cnidium mon-
nieri. Phytochemistry 58, 641–644.