.
I. C¸ alı s¸ et al. / Phytochemistry 59 (2002) 451–457
456
3
cm (C–O–C). H and C NMR (DMSO-d ): Table 1.
407 (OH), 2930 (CH), 1660 (enone), 1075, 1040
À1
mixtures were kept at room temperature over night,
then poured into ice-water and extracted with Et O.
1
13
6
2
After work-up the residues were purified by prep. TLC
(silica gel, hexane–acetone 2:1, R ca. 0.3) to yield the
3
(
.5. Spionoside A (2) ((6S,9S)-6-hydroxyinamoside,
(À)-(6S,9S)-9-O-ꢃ-d-glucopyranosyloxy-6,13-
f
MTPA-esters 1c, 1d and 3c, 3d, respectively (each ca. 2 mg).
1
dihydroxy-3-oxo-ꢀ-ionol))
H NMR (CDCl , 600 MHz) of 1d ((R)-MTPA ester):
3
ꢁ
0.92 (s, Me-12), 1.04 (s, Me-11), 1.44 (d, J=6.5, Me-
2
D
0
ꢀ
Amorphous. ½ꢀ À43.0 (c 0.3, MeOH). ESIMS m/z
10), 1.82 (d, J=1.4, Me-13), 2.19, 2.28 (AB, J=17, H2-
2), 3.56 (q, J=1.2, OMe), 5.65 (quint.-like, J ꢂ 6.5, H-
9), 5.76 (m, H-7, H-8), 5.88 (q, J=1.4, H-4), 7.35–7.42
(3H), 7.49-7.52 (2H) (m, ar-H).
+
4
2
8
1
25 [M+Na] (calc. for C H O ). UV l
(MeOH):
max
1
9
30
9
45 nm. CD ꢀ"
À5
+6.9, ꢀ"315À1.8 (MeOH, c
2
41
.9ꢁ10 M). IR ꢄmax (KBr): 3400 (OH), 2930 (CH),
653 (enone), 1040 cm (C–O–C). H and 13C NMR
À1
1
1
H NMR (CDCl , 600 MHz) of 1d ((S)-MTPA ester):
3
(
DMSO-d ): Table 2.
6
ꢁ 0.97 (s, Me-12), 1.07 (s, Me-11), 1.40 (d, J=6.5, Me-10),
.84 (d, J=1.3, Me-13), 2.23, 2.34 (AB, J=17, H -2),
1
2
3.6. Spionoside B (3) ((9S)-drummondol-9-O-ꢃ-d-
glucopyranoside))
3.51 (q, J < 1, OMe), 5.63 (dq, J=6.5, 6.2, H-9), 5.87
(m, H-7, H-8), 5.91 (q, J=1.3, H-4), 7.36–7.42 (3H),
7
.49–7.52 (2H) (m, ar-H).
1
2
D
0
ꢀ
Amorphous. ½ꢀ À51.2 (c 2.0, MeOH). ESIMS m/z
H NMR (CDCl , 600 MHz) of 3c ((R)-MTPA ester): ꢁ
3
4
25 [M+Na]+ (calc. for C H O ). UV l
(MeOH):
À4
0.94 (s, Me-12), 1.12 (s, Me-13), 1.48 (d, J=6.6, Me-10),
2.34, 2.37 (AB, J=19.8, H -4), 2,48 (d, J=18.2, H -2),
2.56 (dd, J=18.2, 1.5, H -2), 3.55 (q, J < 1, OMe), 3.74 (d,
1
9
30
9
max
2
M). IR ꢄ
09 nm. CD ꢀ"244 +2.3, ꢀ"296À2.3 (MeOH, c 1.0ꢁ10
2
a
À1
(KBr): 3450 (OH), 2925 (CH), 1045 cm (C–
13
max
b
1
O–C). H and C NMR (DMSO-d ): Table 3.
6
J=8.4, H -11), 3.86 (dd, J=8.4, 1.5, H -11), 5.68 (dq,
a
b
J=6.6, 6.0, H-9), 5.88 (d, J=15.2, H-7), 6.12 (dd, J=15.2,
6.0, H-8), 7.36–7.43 (3H), 7.49–7.52 (2H) (m, ar-H).
3
.7. Acetylation of 1 and 3
1
H NMR (CDCl , 600 MHz) of 3d ((S)-MTPA ester): ꢁ
3
Compounds 1 and 3 (each 5 mg) were separately
treated with Ac O and pyridine (each 0.5 ml) at room
0.97 (s, Me-12), 1.19 (s, Me-13), 1.44 (d, J=6.5, Me-10),
2.34, 2.43 (AB, J=19.8, H -4), 2.52 (d, J=18.2, H -2),
2.58 (dd, J=18.2, 1.2, H -2), 3.51 (q, J < 1, OMe), 3.74 (d,
2
2
a
temp. overnight. The reaction mixtures were diluted
with H O (2 ml), adsorbed on an RP-18 cartridge
b
J=8.4, H -11), 3.88 (dd, J=8.4, 2.0, H -11), 5.65 (quint.,
b
2
a
1
(
H O. Elution with CHCl yielded the acetates 1a and
Waters, Sep-Pak Vak) and thoroughly washed with
J=6.5 H-9), 6.00 (d, J=15.2, H-7), 6.19 (dd, J=15.2, 6.5,
H-8), 7.35–7.43 (3H), 7.49–7.52 (2H) (m, ar-H).
2
3
1
3
respectively.
a, respectively. H NMR (CDCl ): see Tables 1 and 3,
3
References
3
.8. Enzymatic hydrolysis of 1 and 3
Achenbach, H., Waibel, R., Raffelsberger, B., Addae-Mensah, I.,
1981. Iridoid and other constituents of Canthium subcordatum.
Phytochemistry 20, 1591–1595.
The solutions of 1 and 3 (each 10 mg) in acetate buffer
Aimi, N., Hoshino, H., Nishimura, M., Sakai, S.-I., Haginiwa, J.,
990. Chaboside, first natural glycocamptothecin found from
(pH 4.4, 10 ml) were treated separately with b-gluco-
sidase (15 mg), and the solutions were left at 37 C for
4
and the residues were separately chromatographed on
silica gel (7 g), using CH Cl –MeOH–H O (90:10:1) to
afford 1a ((9S)-blumenol A, 5 mg) and 3a ((9S)-drum-
1
ꢀ
Ophiorrhiza pumila. Tetrahedron Letters 31, 5169–5172.
Baltenweck-Guyot, R., Trendel, J.-M., Albrecht, P., Schaeffer, A.,
1996. Mono- and diglycosides of (E)-6,9-dihydroxymegastigma-4,7-
dien-3-one in Vitis vinifera wine. Phytochemistry 43, 621–624.
Baytop, T., 1999. Therapy with Medicinal Plants (Past and Present).
Istanbul University Publications, Istanbul.
8 h. The reaction solutions were evaporated to dryness,
2
2
2
1
mondol, 5 mg), respectively. H NMR (CDCl ): Tables 1
3
Bhakuni, D.S., Joshi, P.P., Uprety, H., Kapil, R.S., 1974. Roseoside—
a C1 glycoside from Vinca rosea. Phytochemistry 13, 2541–2543.
and 3, respectively. CD of 1b ꢀ"
À4
+4.1, ꢀ"307À1.4
2
42
3
.
, I., Kuruu
(
ꢀ
MeOH, c 1.3ꢁ10
M). CD of 3a ꢀ"
À5
+0.9,
45
C
¸
alıs¸
cosides from Capparis spinosa fruits. Phytochemistry 50, 1205–1208.
¨
zu
¨
m, A., Ru
¨
edi, P., 1999. 1H-Indole-3-acetonitrile gly-
2
"
À21.7 (MeOH, c 8.3ꢁ10 M).
2
97
Cookson, R.C., Crabb, T.A., Frankel, J.J., Hudec, J., 1966. Geminal
coupling constants in methylene groups. Tetrahedron 22 (Suppl. 7),
3
.9. (R)- and (S)-MTPA esters of 1 and 3
3
55–390.
Davis, P.H., 1965. Flora of Turkey and the East Aegean Islands, Vol.
1. University Press, Edinburgh.
The solutions of the respective aglycones 1 and 3
each 2.5 mg) in CH Cl (1.5 ml) were treated separately
with (R)- and (S)-a-methoxy-a-trifluoromethylphenyl-
acetic acid (MTPA) (25 mg) in the presence of 1-ethyl-3-
Galbraith, N., Horn, D.H.S., 1973. Stereochemistry of the blumenols:
conversion of blumenol A into (S)-(+)-abscisic acid. J. Chem. Soc.
Chem. Commun., 566–567.
(
2
2
Gonza
,5-Dihydroblumenol A, a new nor-isoprenoid from Perrottetia
multiflora. J. Nat. Prod. 57, 400–402.
´
les, A.G., Guillermo, J.A., Ravelo, A.G., Jimenez, I.A., 1994.
(
(
3-dimethylaminopropyl)carbodiimide hydrochloride
21 mg) and 4-dimethylaminopyridine (13 mg). The
4