Three secoiridoid glucosides from Jasminum nudiflorum

Article abstract of DOI:10.1021/np9901175

Phytochemical study of the leaves and stems of Jasminum nudiflorum has led to the isolation of three secoiridoid glucosides, jasnudiflosides A-C (1- 3). The structures of these compounds were elucidated on the basis of chemical and spectroscopic evidence.

Full text of DOI:10.1021/np9901175

J . Nat. Prod. 1999, 62, 1311-1315
1311
Th r ee Secoir id oid Glu cosid es fr om J a sm in u m n u d iflor u m
Takao Tanahashi,*,† Yukiko Takenaka,† Naotaka Nagakura,† and Toyoyuki Nishi‡
Kobe Pharmaceutical University, 4-19-1, Motoyamakita-machi, Higashinada-ku, Kobe 658-8558, J apan, and The Nippon
Shinyaku Institute for Botanical Research, 39, Sakanotsuji-cho, Oyake, Yamashina-ku, Kyoto 607-8182, J apan
Received March 26, 1999
Phytochemical study of the leaves and stems of J asminum nudiflorum has led to the isolation of three
secoiridoid glucosides, jasnudiflosides A-C (1-3). The structures of these compounds were elucidated on
the basis of chemical and spectroscopic evidence.
J asminum nudiflorum Lindl. (Oleaceae) is a shrub
indigenous to China. Its flowers and leaves have been used
as crude drugs in Chinese folk medicine.1 Previous phy-
tochemical studies of the species resulted in isolation of
caffeic glycoside esters.2 In the course of our chemical
studies on the secoiridoid glucosides from oleaceous plants,3
we have investigated the leaves and stems of J . nudiflo-
rum. We report here the isolation and structure elucidation
of three glucosides (1-3), each consisting of oleoside units
and a cyclopentanoid monoterpene unit.
F igu r e 1. Significant NOESY correlations for 12 and ∆δ values of 11
and 12.
Compound 1 was isolated as an amorphous powder. The
HRSIMS of 1 established its elemental composition as
C44H64O23. On conventional acetylation, 1 gave a nona-
acetate (4) C62H82O32. Distinctive 1H NMR spectral features
of 1 (see Table 1) indicated that the isolated compound
possessed two sets of oleoside 11-methyl ester (5) moieties.
The 1H NMR spectrum displayed additional signals for two
secondary methyl groups (δ 0.93 and 0.99, both d, J ) 7.0
Hz), two pairs of oxymethylene protons (δ 3.96, 4.21 and δ
3.34, 3.59), and a methine group bearing an acyloxyl group
(δ 5.04, td, J ) 5.5, 4.0 Hz). Its 13C NMR spectrum showed
resonances of 10 carbons in addition to the duplicated
signals corresponding to the oleoside 11-methyl ester
moieties. With the aid of 1H-1H COSY, HMQC, and HMBC
experiments, these 10 carbon signals were evaluated as a
triol moiety with the same planar structure as triol 6, also
seen as part of jasminin (7)4 and jasmesoside.5 In the
NOESY spectrum of 1, significant interactions were ob-
served between H-1′′ and H-3′′, between H-2′′ and H-6′′,
and between H-7′′ and H-9′′. However, alkaline hydrolysis
of 1 afforded a triol and oleoside (8), of which the former
was not identical to 6, implying the relative stereochem-
istry of the triol in 1 to be 9 rather than 6.
confirmed when triol 6 derived from jasminin (7) was
subjected to a Mitsunobu reaction8 to provide acetate 13,
which differed from acetate 14 but proved identical to the
acetate of 9. Thus, 1 has the structure shown and is named
jasnudifloside A.
The second glucoside (2), named jasnudifloside B, was
also isolated as an amorphous powder, with molecular
1
formula C61H86O33. The H and 13C NMR spectral features
of 2 resembled those of 1, except that 2 demonstrated
signals for an additional oleoside 11-methyl ester (5) unit.
The downfield shift of H-10′′ and C-10′′ and the upfield shift
of C-8′′ in 2, relative to the corresponding signals in 1,
showed that in 2, the C-7 carboxyl group of the additional
oleoside 11-methyl ester moiety was linked to the C-10′′
1
hydroxyl group of the triol moiety. The H and 13C NMR
signals corresponding to the triol moiety in 2 were coinci-
dent with those of 13, indicating that the stereochemistry
of the triol moiety in 2 was the same as in 1. Accordingly,
the structure of 2 was established as shown.
HRSIMS of jasnudifloside C (3) established the composi-
tion as C43H60O22. Its 1H and 13C NMR spectral features
(Tables 1 and 2) clearly demonstrated the presence of a
triol (9) moiety and two oleoside units, of which one
contained a methylated carboxyl group. This assumption
was supported by hydrolysis of 3, which afforded oleoside
and triol 9. The pattern of ester linkages was determined
by a combination of 1H-1H COSY, HMQC, and HMBC
experiments, which allowed assignment of the signals from
H-7′′ and H-10′′ as well as the signals of the carbonyls C-7a,
C-7b, C-11a, and C-11b. The HMBC experiments with 3
showed strong interactions between H-7′′ and C-7a (δ
173.36), between OMe and C-11a (δ 168.62), and between
H-10′′ and C-11b (δ 168.78). Accordingly, the structure of
jasnudifloside C is 3.
1
The H and 13C NMR spectral features of 1 were in good
agreement with those reported for jasuroside A (10), which
had been isolated from J . urophyllum by Shen et al.,6
except for the assignments of H-2′′ and H-3′′. The absolute
stereochemistry of 10 was deduced solely using its NOESY
spectrum. This prompted us to establish the absolute
stereochemistry of 1 by chemical evidence. To determine
the absolute configuration at C-5′′ in triol 9 by a modifica-
tion of Mosher’s method,7 its (R)- and (S)-MTPA esters
(11,12) were prepared. The NOESY experiments with 12
confirmed the relative configurations at C-1′′, C-2′′, C-3′′
and C-5′′ (Figure 1). The ∆δ values of the MTPA derivatives
determined the absolute configuration of C-5′′ to be S,
indicating 9 to be the 5′′-epimer of triol 6. This was
* To whom correspondence should be addressed. Fax:+81-78-441-7546;
E-mail: tanahash@kobepharma-u.ac.jp.
Oleoside-type secoiridoid glucosides esterified with a
cyclopentanoid monoterpene have so far been found only
in species of the genus J asminum, that is; J . mesnyi,4,5,9,10
† Kobe Pharmaceutical University.
‡ The Nippon Shinyaku Institute for Botanical Research.
10.1021/np9901175 CCC: $18.00
© 1999 American Chemical Society and American Society of Pharmacognosy
Published on Web 08/05/1999

Ta ble 1. 1H NMR Spectral Data for 1-4 (500 MHz)a
1b
2b,d
3b
4c,d
H
a part
5.96, br s
b part
5.95, br s
a part
5.93, br s
b part
c part
5.96, br s
a part
5.95, br s
b part
5.87, br s
a part
b part
5.73, br s
1
3
5
6
5.95, br s
5.71, br s
7.46, s
7.53, s
7.53, s
7.52, s
7.53, s
7.53, s
7.54, s
7.43, s
7.47, s
4.00, dd (9.0, 4.5)
4.00, dd (9.0, 4.5)
3.97-4.03, m
3.97-4.03, m
3.97-4.03, m
4.01, dd (9.5, 4.5)
3.99, dd (9.5, 4.5)
2.37, dd (14.0, 4.5) 2.45, dd (15.0, 8.0)
2.45, dd (14.0, 9.5) 2.69, dd (15.0, 4.5)
6.07, qd (7.0, 1.0)
1.82, dd (7.0, 1.0)
3.97, m
3.97, m
2.52, dd (14.0, 9.0) 2.52, dd (14.0, 9.0) 2.49, dd (14.0, 9.0) 2.51, dd (14.0, 9.0) 2.52, dd (14.0, 9.0) 2.54, dd (14.0, 9.0)
2.73, dd (14.0, 4.5) 2.70, dd (14.0, 4.5) 2.70, dd (14.0, 4.5) 2.72, dd (14.0, 4.5) 2.73, dd (14.0, 4.5) 2.73, dd (14.0, 4.5)
6.11, qd (7.0, 1.0)
1.75e, dd (7.0, 1.0)
3.72, s
4.80, d (8.5)
3.27-3.41, m
2.47, dd (15.0, 8.5)
2.70, dd (15.0, 4.5)
6.01, br q (7.0)
1.76, dd (7.0, 1.5)
3.72, s
8
10
OMe
1′
2′-4′
5′
6.12, qd (7.0, 1.0)
1.76e, dd (7.0, 1.5)
3.72, s
4.81, d (7.5)
3.27-3.41, m
6.10, qd (7.0, 1.0)
1.74, dd (7.0, 1.0)
3.71, s
4.80, d (7.5)
3.28-3.41, m
6.12, qd (7.0, 1.0)
1.75, dd (7.0, 1.0)
3.72, s
4.80, d (8.0)
3.28-3.41, m
6.13, qd (7.0, 1.0)
1.76, dd (7.0, 1.0)
3.72, s
4.81, d (7.5)
3.28-3.41, m
6.13, qd (7.0, 1.0)
1.75, dd (7.0, 1.0)
3.72, s
4.81, d (8.0)
3.27-3.41, m
6.01, br q (7.0)
1.75, dd (7.0, 1.5)
3.72, s
5.03, d (8.0)
5.03-5.28, m
3.764, dd (9.5, 4.5,
2.5)
4.81, d (8.0)
3.27-3.41, m
5.04, d (8.0)
5.03-5.28, m
3.765, ddd (9.5,
4.5, 2.5)
4.11, dd (12.5, 2.5)
4.33, dd (12.5, 4.5)
}
}
}
}
}
}
6′
3.65f, dd (12.0, 6.0) 3.66f, dd (12.0, 6.0) 3.65, dd (12.0, 6.0) 3.66, dd (12.0, 6.0) 3.66, dd (12.0, 6.0) 3.64h, dd (11.5, 6.0)
3.67h, dd (12.0, 6.5) 4.00, dd (12.5, 2.5)
3.89g, dd (12.0, 2.0) 3.90g, dd (12.0, 2.0) 3.91, dd (12.0, 2.0) 3.87, dd (12.0, 2.0) 3.87, dd (12.0, 2.0) 3.88i, dd (11.5, 1.5)
3.90i, dd (12.0, 2.0) 4.31, dd (12.5, 4.5)
1′′
2′′
3′′
4′′
1.96, m
1.84, m
1.81, m
1.62, ddd (14.0,
5.5, 4.0)
1.94, m
1.85, m
1.85, m
1.64, ddd (14.0, 4.0,
3.0)
1.81, m
1.91, m
1.81, m
1.90, m
1.79, m
1.71, m
2.01, br dd (11.0, 4.5)
1.59, m (14.5, 6.5, 4.0)
2.08, ddd (14.0,
9.0, 5.5)
2.09, ddd (14.0, 9.0,
5.0)
2.01, br dd (11.0, 4.5)
2.00, m
5′′
6′′
7′′
5.04, td (5.5, 4.0)
0.93, d (7.0)
3.96, dd (11.5, 5.0)
4.21, dd (11.5, 4.0)
1.66, ddd (14.0,
7.0, 4.0)
5.05, td (4.5, 2.0)
0.94, d (7.0)
3.99, m
4.19, dd (11.0, 3.5)
1.90, m
4.91, br t (3.5)
1.00, d (6.5)
4.08, dd (11.5, 4.5)
4.19, dd (11.5, 4.5)
2.08, m
5.06, br q (4.5)
0.90, d (7.0)
3.95, m
4.10, m
1.85, m
8′′
9′′
10′′
0.99, d (7.0)
3.34, m
3.59, dd (10.0, 4.5)
1.00, d (6.5)
3.75, dd (11.0, 7.0)
4.16, dd (11.0, 4.5)
0.97, d (7.0)
4.12, m (11.5, 3.5)
4.34, dd (11.4, 9.0)
0.97, d (7.0)
3.80, dd (11.5, 8.5)
4.07, dd (11.5, 4.5)
2.025 (×2), 2.031, 2.035,
(×2), 2.042 (×2), 2.08,
2.09 s
Ac
a
b
d
Chemical shifts are reported in ppm. Values in parentheses are coupling constants in Hz. Measured in CD3OD. c Measured in CDCl3. All signals due to the oleoside 11-methyl ester units
e-i
could not be assigned with certainty and may be interchanged horizontally.
Assignments may be reversed.

Notes
J ournal of Natural Products, 1999, Vol. 62, No. 9 1313
Multisolvent Delivery System, 486 tunable absorbance detec-
tor). TLC was performed on Kieselgel 60F254 plates (Merck),
and spots were visualized under UV light.
P la n t Ma ter ia l. Leaves and stems of J . nudiflorum were
collected at the Nippon Shinyaku Institute for Botanical
Research, Kyoto, J apan. A voucher specimen (KPFY 991) is
deposited at the laboratory of Kobe Pharmaceutical University.
Isola t ion of Glu cosid es. Dried leaves and stems of J .
nudiflorum (128 g) were extracted with hot MeOH. After
concentration, the extract (20.6 g) was suspended in H2O and
filtered through a Celite layer. The filtrate and washings were
combined and extracted successively with CHCl3 and n-BuOH,
to give three fractions weighing 1.54 g (CHCl3), 6.21 g
(n-BuOH), and 8.72 g (H2O). The CHCl3-soluble fraction was
chromatographed on a Si gel column, eluting with CHCl3-
MeOH mixtures with increasing MeOH content (5-20%).
Elution with 10% MeOH-CHCl3 gave three fractions I (152
mg), II (192 mg), and III (639 mg). Fraction II was further
purified by preparative HPLC (µBondasphere 5 µC18-100 Å,
MeOH-H2O, 3:2), giving 3 (151 mg). Fraction III was also
purified by preparative HPLC (µBondasphere 5 µC18-100 Å,
MeOH-H2O, 3:2) to afford 1 (228 mg), 2 (16.8 mg), and 3 (196
mg).
J a sn u d iflosid e A (1): colorless amorphous powder; [R]20
D
-192° (c 0.78, MeOH); UV (MeOH) λmax (log ꢀ) 237 (4.38) nm;
IR (KBr) νmax 3406, 1732, 1709, 1632, 1078 cm-1; 1H NMR and
13C NMR, see Tables 1 and 2; significant HMBC correlations
H-6a (δ 2.73) f C-7a (δ 173.41), H2-7′′ f C-7a, OMe f C-11a/
C-11b, H-6b (δ 2.70) f C-7b (δ 172.98), H3-6′′ f C-1′′/C-2′′,
H2-10′′ f C-9′′; SIMS m/z 959 [M - H]-, 797, 727, 421;
HRSIMS m/z 959.3771 [M - H]- (calcd for C44H63O23, 959.3762).
J a sn u d iflosid e B (2): colorless amorphous powder; [R]24
D
-206° (c 0.68, MeOH); UV (MeOH) λmax (log ꢀ) 237 (4.56) nm;
IR (KBr) νmax 3414, 1732, 1709, 1636, 1078 cm-1; 1H NMR and
13C NMR, see Tables 1 and 2; significant HMBC correlations
OMe f C-11a, C-11b, C-11c; SIMS m/z 1345 [M - H]-, 1183,
1114; HRSIMS m/z 1345.4984 [M - H]- (calcd for C61H85O33
1345.4976).
,
J a sn u d iflosid e C (3): colorless amorphous powder; [R]22
D
-238° (c 0.31, MeOH); UV (MeOH) λmax (log ꢀ) 237 (4.39) nm;
IR (KBr) νmax 3400, 1728, 1709, 1630, 1078 cm-1; 1H NMR and
13C NMR, see Tables 1 and 2; significant HMBC correlations
H-3a f C-4a (δ 109.39)/C-11a (δ 168.62), H-6a f C-4a/C-7a
(δ 173.36), H2-7′′ f C-7a, OMe f C-11a, H-3b f C-4b (δ
111.27)/C-11b (δ 168.78), H-6b f C-4b/C-7b (δ 173.63), H3-6′′
f C-1′′/C-2′′/C-5′′, H3-9′′ f C-3′′/C-8′′/C-10′′, H2-10′′ f C-11b;
SIMS m/z 927 [M - H]-, 765, 695; HRSIMS m/z 927.3513 [M
- H]- (calcd for C43H59O22, 927.3500).
Acetyla tion of 1. Compound 1 (15.0 mg) was acetylated
with Ac2O-pyridine, and the crude acetate (19.1 mg) was
purified by preparative TLC (CHCl3) to yield 4 (18.0 mg) as
an amorphous powder: [R]24 -148° (c 1.27, CHCl3); UV
D
(EtOH) λmax (log ꢀ) 235 (4.38) nm; IR (KBr) νmax 1759, 1709,
1
1635, 1070 cm-1; H NMR and 13C NMR, see Tables 1 and 2;
HRSIMS m/z 1361.4722 [M + Na]+ (calcd for C62H82O32Na,
1361.4690), 1339.4892 [M
1339.4870).
+ ,
H]+ (calcd for C62H83O32
Alk a lin e Hyd r olysis of 1 a n d 3. A solution of 1 (50 mg)
in 0.5M NaOH (2 mL) was stirred for 18 h at room tempera-
ture. The reaction mixture was neutralized with Amberlite IR-
120 (H+ form) and concentrated in vacuo. The resulting residue
was purified by preparative TLC (CHCl3-MeOH, 9:1) to 8 (43
mg) and triol 9 (6.5 mg).
J . urophyllum, J . sambac,11,12 and J . azoricum.13,14 The
present work gives additional examples of glucosides of this
type.
Exp er im en ta l Section
Com p ou n d 9: syrup; [R]23D -7.9° (c 0.67, MeOH); 1H NMR
(500 MHz, CDCl3) δ 0.97 (3H, d, J ) 6.5 Hz, H3-9′′), 0.99 (3H,
d, J ) 7.0 Hz, H3-6′′), 1.53 (1H, ddd, J ) 12.5, 7.0, 5.5 Hz,
H-4′′), 1.66 (3H, m, H-2′′, H-3′′, H-8"), 1.86 (1H, qt, J ) 7.0,
6.0 Hz, H-1′′), 1.91 (1H, ddd, J ) 12.5, 8.0, 5.5 Hz, H-4′′), 3.37
(1H, dd, J ) 11.0, 7.0 Hz, H-10′′), 3.48 (1H, dd, J ) 11.5, 5.5
Hz, H-7′′), 3.55 (1H, dd, J ) 11.5, 4.0 Hz, H-7′′), 3.60 (1H, dd,
Gen er a l Exp er im en ta l P r oced u r es. The UV spectra
were recorded on a Shimadzu UV-240 spectrophotometer and
the IR spectra on a Shimadzu FTIR-8200 infrared spectro-
photometer. The optical rotations were measured on a J ASCO
DIP-370 digital polarimeter. CIMS, SIMS, and HRSIMS were
obtained with a Hitachi M-4100 mass spectrometer. For SIMS,
glycerol or 3-NOBA was used as the matrix. The NMR
experiments were performed with Varian VXR-500 and Varian
Gemini-300 spectrometers, with TMS as internal standard.
J ) 11.0, 5.0 Hz, H-10′′), 4.03 (1H, br q, J ) 5.5 Hz, H-5′′); 13
C
NMR, see Table 2.
Com p ou n d 8: methylated with CH2N2-Et2O and the
HPLC separations were run on
a
Waters system (600E
product identified as oleoside dimethyl ester15 (1H NMR).

1314 J ournal of Natural Products, 1999, Vol. 62, No. 9
Notes
Ta ble 2. 13C NMR Spectral Data for 1, 2, 3, 4, 9, and 13 (125 MHz)
1a
2a,c
3a
4b,c
C
a part
b part
a part
b part
c part
a part
b part
a part
b part
9b
13a
13b
1
3
4
5
6
7
8
9
95.22
155.18d
109.42
32.15
94.82
155.25d
109.42
31.93
94.84
155.16
109.40
31.90
41.27
173.00
124.77
130.79
13.79
168.63
52.01
100.57
74.83
77.98
71.54
78.47
62.86
41.86
48.05
43.32
34.95
80.15
13.91
66.83
37.47
16.87
69.14
95.21
155.19
109.41
31.93
95.29
155.23
109.44
31.18
94.82
155.20
109.39
32.16
95.16
153.26
111.27
31.66
93.74
153.01
108.63
30.15
39.97
170.89
124.73
128.40
13.58
166.71
51.40
97.02
70.74
72.22
68.29
72.55
61.74
40.42
46.75
42.04
33.86
77.79
13.47
66.00
36.18
16.28
67.49
20.59q
20.62q
20.67q
169.34
169.35
169.40q
170.19q
93.87
153.07
108.63
30.20
40.02
171.07
124.78
128.54
13.63
166.76
51.44
97.09
70.74
72.27
68.29
72.56
61.80
41.52
41.25
41.27
41.65
41.21
43.90
173.41
124.79
130.84
13.73e
168.64f
51.96g
100.84
74.84
172.98
124.79
130.76
13.83e
168.69f
51.98g
100.54
74.84
173.29
124.77
130.83
13.82
168.63
52.01
100.87
74.83
77.98
173.39
124.81
130.90
13.86
168.66
52.01
100.90
74.85
78.00
173.36
124.74
130.81
13.73
168.62
51.95
100.55
74.80k
77.98l
71.60m
78.48n
62.78o
42.37
173.63
123.60
132.30
13.23p
168.78
10
11
OMe
1′
2′
3′
4′
5′
6′
1′′
2′′
3′′
4′′
5′′
6′′
7′′
8′′
9′′
100.89
74.87k
78.01l
71.71m
78.66n
62.97o
77.97h
71.62i
78.54j
62.94
41.83
48.11
42.60
35.39
80.06
14.15
78.01h
71.69i
78.63j
62.94
71.61
78.50
62.93
71.71
78.64
63.00
42.32
51.23
42.27
37.02
75.73
14.25
65.42
41.10
16.53
66.70
42.31
48.08
43.75
34.72
79.63
13.67
67.27
37.40
16.61
68.83
20.81
20.85
21.06
172.61
172.93
172.99
40.89
46.64
42.33
33.84
77.67
13.39
66.05
36.01
16.36
67.54
20.94q
20.97
50.61
46.31
31.95
82.17
13.20p
66.65
67.22
41.07
16.32
66.47
37.11
19.21
67.86
10′′
CH3CO
20.72q
20.95
CH3CO
170.54
170.57
171.23
170.75
171.15
171.17
a
b
Measured in CD3OD. Measured in CDCl3. c All carbon signals due to the oleoside 11-methyl ester units could not be assigned with
d-p
q
certainty and may be interchanged horizontally.
Values with the same superscript are interchangeable. Two-carbon signals.
A solution of 3 (52 mg) in 0.5 M NaOH (2 mL) was stirred
for 24 h at room temperature. The reaction mixture was
worked up in the same way as for 1, giving oleoside16 (40.4
1.0 Hz, 3 × OMe), 3.893 (1H, dd, J ) 12.5, 6.5 Hz, H-10′′),
4.128 (1H, dd, J ) 12.0, 4.5 Hz, H-7′′), 4.210 (1H, dd, J ) 12.5,
3.5 Hz, H-10′′), 4.350 (1H, dd, J ) 12.0, 3.0 Hz, H-7′′), 5.274
(1H, td, J ) 5.0, 2.5 Hz, H-5′′), 7.37-7.50 (15H, m, ArH); SIMS
m/z 859 [M + Na]+.
mg) and triol 9 (9.9 mg), [R]24 -6.6° (c 0.78, MeOH).
D
Acetyla tion of 9. Compound 9 (18 mg) was acetylated with
Ac2O-pyridine and the crude acetate was purified by prepara-
tive HPLC (µBondasphere 5 µC18-100 Å, MeOH-H2O, 3:2)
Triol 9 (3.6 mg) was esterified with (S)-MTPA acid in the
same way described for 11 to yield 12 (11.3 mg).
to yield 13 (7.8 mg).
Com p ou n d 12: syrup; 1H NMR (500 MHz, CDCl3) δ 0.812
(3H, d, J ) 6.5 Hz, H3-9′′), 0.915 (3H, d, J ) 7.0 Hz, H3-6′′),
1.434 (1H, ddd, J ) 15.0, 5.5, 2.5 Hz, H-4′′), 1.489 (1H, m,
H-8′′), 1.560 (1H, m, H-3′′), 1.710 (1H, m, H-2′′), 1.870 (1H, m,
H-1′′), 1.948 (1H, ddd, J ) 15.0, 9.5, 5.0 Hz, H-4′′), 3.485, 3.497,
3.531 (each 3H, d, J ) 1.0 Hz, 3 × OMe), 3.850 (1H, dd, J )
11.5, 6.5 Hz, H-10′′), 3.962 (1H, dd, J ) 11.5, 4.0 Hz, H-10′′),
4.301 (2H, d, J ) 3.5 Hz, H2-7′′), 5.188 (1H, td, J ) 5.0, 2.5
Hz, H-5′′), 7.42-7.58 (15H, m, ArH); SIMS m/z 859 [M + Na]+.
Acetyla tion of 6. Triol 6 (12.8 mg) obtained from jasminin
(7) by hydrolysis as described by Inoue et al.5 was acetylated
with Ac2O-pyridine and the crude acetate (15.6 mg) was
purified by preparative HPLC (µBondasphere 5 µC18-100 Å,
MeOH-H2O, 11:9) to yield 14 (8.4 mg): 1H NMR (300 MHz,
CDCl3) δ 1.00 (3H, d, J ) 6.5 Hz, H3-9′′), 1.04 (3H, d, J ) 7.0
Hz, H3-6′′), 1.68 (1H, m, H-1′′), 1.80-1.94 (5H, m, H-2′′, H-3′′,
H2-4′′, H-8′′), 2.03, 2.06, 2.07 (each 3H, s, Ac), 3.89 (1H, dd, J
) 11.0, 6.5 Hz, H-10′′), 4.01 (1H, dd, J ) 11.5, 6.5 Hz, H-7′′),
4.04 (1H, dd, J ) 11.0, 4.5 Hz, H-10′′), 4.12 (1H, dd, J ) 11.5,
5.0 Hz, H-7′′), 4.72 (1H, br q, J ) 4.5 Hz, H-5′′).
1
Com p ou n d 13: [R]27 +3.4° (c 0.78, CHCl3); H NMR (500
D
MHz, CDCl3) δ 0.98 (3H, d, J ) 7.5 Hz, H3-6′′), 0.99 (3H, d, J
) 6.5 Hz, H3-9′′), 1.62 (1H, ddd, J ) 14.0, 6.5, 3.0 Hz, H-4′′),
1.76 (1H, ddt, J ) 8.5, 8.0, 6.5 Hz, H-3′′), 1.86-1.96 (3H, m,
H-1′′, H-2′′, H-8′′), 2.055, 2.060, 2.067 (each 3H, s, Ac), 2.07
(1H, ddd, J ) 14.0, 10.0, 5.5 Hz, H-4′′), 3.83 (1H, dd, J ) 11.0,
7.5 Hz, H-10′′), 4.06 (1H, dd, J ) 11.5, 5.5 Hz, H-7′′), 4.10 (1H,
dd, J ) 11.0, 5.0 Hz, H-10′′), 4.13 (1H, dd, J ) 11.5, 4.5 Hz,
H-7′′), 5.08 (1H, td, J ) 5.5, 3.0 Hz, H-5′′); CIMS m/z 315 [M
+ H]+.
(R)- a n d (S)-MTP A Ester s of 9. To a solution of 9 (3.8
mg) in dry CH2Cl2 (1 mL) were added (R)-MTPA acid (7 mg),
DMAP (3 mg), and DCC (10 mg), and the whole was stirred
for 7 h at room temperature. Then more (R)-MTPA acid (20
mg) and DCC (20 mg) were added, and the reaction mixture
was stirred for an additional 18 h. The reaction mixture was
diluted with H2O and extracted with CHCl3, and was then
washed and dried. The organic layers were concentrated in
vacuo, and the resulting residue was purified by successive
preparative TLC (Et2O), column chromatography on Sephadex
LH-20 (CHCl3-MeOH, 10:9), and preparative TLC (Et2O-n-
hexane, 1:1), giving 11 (11.0 mg).
Mitsu n obu Rea ction of 6. Triol 6 (57.0 mg), Ph3P (800
mg), and HOAc (172 µL) were mixed in dry THF (3 mL).
Diethyl azodicarboxylate (DEAD; 800 µL) was added dropwise
to the solution, and the mixture was kept at room temperature
for 6.5 h. Then the same amounts of all reagents were added
once more. After an additional 19.5 h, the solution was
evaporated in vacuo and the residue purified by preparative
TLC (CHCl3-MeOH, 19:1) and preparative HPLC (µBondas-
Com p ou n d 11: syrup; 1H NMR (500 MHz, CDCl3) δ 0.779
(3H, d, J ) 7.0 Hz, H3-9′′), 0.865 (3H, d, J ) 6.5 Hz, H3-6′′),
1.546 (1H, ddd, J ) 14.5, 5.5, 2.5 Hz, H-4′′), 1.61-1.72 (3H,
m, H-2′′, H-3′′, H-8′′), 1.824 (1H, m, H-1′′), 2.008 (1H, ddd, J
) 14.5, 8.5, 5.0 Hz, H-4′′), 3.479, 3.485, 3.506 (each 3H, d, J )

Notes
J ournal of Natural Products, 1999, Vol. 62, No. 9 1315
(6) Shen, Y.-C.; Hsieh, P.-W. J . Nat. Prod. 1997, 60, 453-457.
(7) Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J . Am. Chem.
Soc. 1991, 113, 4092-4096.
phere 5 µC18-100 Å, MeOH-H2O, 11:9), giving 13 (7.7 mg),
[R]27 +3.0° (c 0.62, CHCl3); CIMS m/z 315 [M + H]+.
D
(8) Mitsunobu, O.; Eguchi, M. Bull. Chem. Soc. J pn. 1971, 44, 3427-
Ack n ow led gm en t. Thanks are due to Dr. M. Sugiura
3430.
1
(Kobe Pharmaceutical University) for H and 13C NMR spectra
(9) Inoue, K.; Fujita, T.; Inouye, H.; Kuwajima, H.; Takaishi, K.;
Tanahashi, T.; Nagakura, N.; Asaka, Y.; Kamikawa, T.; Shingu, T.
Phytochemistry 1991, 30, 1191-1201.
and to Dr. K. Saiki (Kobe Pharmaceutical University) for MS
measurements.
(10) He, Z.-D.; Yang, C.-R. Acta Bot. Yunnan 1989, 11, 55-59.
(11) Tanahashi, T.; Nagakura, N.; Inoue, K.; Inouye, H. Tetrahedron Lett.
1988, 29, 1793-1796.
Refer en ces a n d Notes
(12) Zhang, Y.-J .; Liu, Y.-Q.; Pu, X. Y.; Yang, C.-R. Phytochemistry 1995,
38, 899-903.
(1) Chiang Su New Medical College, (Eds.) Zhong-Yao-Dai-Ci-Dian
(Dictionary of Chinese Crude Drugs); Shanghai Scientific Technologic
Publisher: Shanghai, 1978; p 1156.
(2) Andary, C.; Tahrouch, S.; Marion, C.; Wylde, R.; Heitz, A. Phytochem-
istry 1992, 31, 885-886.
(3) Tanahashi, T.; Parida; Takenaka, Y.; Nagakura, N.; Inoue, K.;
Kuwajima, H.; Chen, C.-C. Phytochemistry 1998, 49, 1333-1337, and
references therein.
(13) Ross, S. A.; Abdel-Hafiz, M. A.; Ali, A. A. Egypt. J . Pharm. Sci. 1986,
27, 221-226.
(14) Somanadhan, B.; Wagner Smitt, U.; George, V.; Pushpagadan, P.;
Rajasekharan, S.; Duus, J . O.; Nyman, U.; Olsen, C. E.; J aroszewski,
J . W. Planta Med. 1998, 64, 246-250.
(15) Damtoft, S.; Franzyk, H.; J ensen, S. R. Phytochemistry 1992, 31,
4197-4201.
(4) Kamikawa, T.; Inoue, K.; Kubota, T.; Woods, M. C. Tetrahedron 1970,
26, 4561- 4587.
(16) Damtoft, S.; Franzyk, H.; J ensen, S. R. Phytochemistry 1995, 40,
773-784.
(5) Inoue, K.; Tanahashi, T.; Inouye, H. Phytochemistry 1985, 24, 1299-
1303.
NP9901175