proton at δ 4.89 (1H, d, J ) 7.6), in agreement with a
structure of a cycloartane triterpene glycoside.
The DEPT spectrum exhibits a set of signals corresponding
Table 1. 1H and 13C NMR Data of Cimicifugadine (1)a
no.
δ
H
*
δ
C
*
δ
H
δ
C
to a pentose moiety [δ
(d, C-3′), 72.1 (d, C-4′), and 68.0 (t,C-5′)], coincided with a
spin-sysyem consisting of H1′-H2′-H3′-H4′-H 5′, sug-
C
108.4 (d, C-1′), 79.5 (d, C-2′), 76.5
1
2
2.76 (â) (d, 14.0),
28.3 t 2.15 (â) (dd, 3.4,
27.0 t
29.2 t
b
a
1.75 (R)
13.5), 1.37(R)
30.8 t 1.53 (R) (m),
b
b
2.10 (R), 2.43 (â)
2
1
.80 (â) (m)
gesting the presence of xylose or arabinose. The typical large
coupling constants between H-1′ and H-2′ (JH1′-H2′ ) 7.6
Hz), H-2′ and H-3′ (JH2′-H3′ ) 8.2 Hz), and H-3′ and H-4′
3
4
5
6
3.60 (R) (brd, 11.5)
1.37 (R)b
89.3 d 3.14 (dd, 4.0, 11.5)
41.7 s
87.6 d
40.4 s
43.6 d
21.7 t
44.9 d 1.12 (dd, 5.2, 12.2)
23.0 t 1.91 (R) (m),
b
b
1.75 (â), 1.96 (R)
1
.67 (â) (t, 14.4)
(JH3′-H4′ ) 8.2 Hz) indicated that the protons at C-1′, C-2′,
7
8
9
1
1
1
1
5.32 (d, 7.7)
115.8 d 5.23 (dd, 6.4, 1.6)
147.3 s
114.4 d
146.3 s
26.9 s
28.9 s
62.4 d
C-3′, and C-4′ have an axial, equatorial, axial, equatorial
configuration, which means the hydroxyl groups at C-2′,
C-3′, and C-4′ are in the R-, â-, and R-orientations, as found
28.7 s
30.4 s
0
1
4.60 (R) (d, 8.0)
64.0 d 4.11 (R) (m)
4.78 (d, 6.1)
1-OH nd
4
b
in â-D-xylopyranoside. Thus, the sugar moiety must be either
2
2.43 (â), 3.06 (R)
t, 12.8)
45.4 t 2.80 (R) (dd,
9.5, 13.1)
43.5 t
1
(
â-L-xylopyranosyl [ C
chair conformation] or â-D-xylopy-
4
2
.01 (â) (dd,
4
1
ranosyl [ C chair conformation], with the latter being more
2
.7, 14.0)
1
1
1
3
4
5
49.6 s
52.3 s
48.2 s
50.9 s
43.6 t
favorable as it is a common component of the triterpene
glycoside isolated from Cimicifuga plants, whereas the
isolation of the former has not been reported. The glycon
moiety of 1 was conclusively determined as â-D-xylopyra-
b
2.83 (â) (d, 15.5),
.23 (R) (d, 15.5)
45.0 t 2.95 (â), 2.55 (R)
(d, 15.3)
3
1
1
1
1
6
7
8
9
163.4 s
142.8 s
161.7 s
141.3 s
24.3 q
18.4 t
1.35 (s)
25.3 q 1.15 (s)
19.8 t 1.47 (d, 3.4)
0.75 (d, 3.4)
1
13
nosyl by comparison of its H and C NMR data with those
1.02 (d, 3.4),
reported in the literatures which were found identical.2
2.01 (d, 3.4)
2
2
2
2
2
2
2
2
2
2
2
2
3
1
2
3
4
5
0
1
2
3
4
143.5 s
142.0 s
18.6 q
122.1 d
159.7s
79.1 d
Further evidence for the absolute configuration of sugar was
2.20 (s)
7.56a
19.3 q 2.28 (s)
123.7d 7.05 (s)
161.2 s
25
based on the optical rotation [R]
D
2
+90 (c 0.5, H O)
determined for xylose obtained from acidic hydrolysis.
5.05(â) (s)
80.5 d 4.26(â) (d, 5.4)
5.26 (d, 5.3)
4-OH nd
5
Other signals are for four oxygenated carbons resonating
at δ 89.3 (d), 80.5 (d), 74.6 (s), and 64.0 (d) as well as seven
olefinic carbons resonating at δ 163.4 (s), 161.2 (s), 147.3
(s), 143.5 (s), 142.8 (s), 123.7 (d), and 115.8 (d). All of the
aforementioned evidence suggests that 1 is a 9,19-cycloartane
74.6 s
72.8 s
5-OH nd
4.88 (s)
6
7
8
9
0
′
1.51 (s)
26.9 q 0.93 (s)
28.6 q 1.04 (s)
25.9 q
27.2 q
28.7 q
25.7 q
14.4 q
106.3 d
74.3 d
77.2 d
70.1 d
66.1 t
1.64 (s)
b
1.06 (s)
29.6 q 0.85
1.42 (s)
26.8 q 1.02 (s)
b
1.16 (s)
15.5 q 0.85
4.89 (d, 7.6)
4.04 (t, 8.2)
4.17 (t, 8.2)
4.22 (m)
108.4 d 4.16 (d, 7.6)
triterpene xyloside based on the similarity of its NMR
b
′
76.5 d 2.98
spectral profiles with those reported for other congeners.4
′
79.5 d 3.08 (t, 8.5)
72.1 d 3.27 (m)
68.0 t 3.66 (dd, 5.2, 11.2)
3.02b
′
′
3.73 (t, 11.2)
4.32 (dd, 5.2, 11.2)
a
1
13
NMR (600 MHz for H and 150 MHz for C) were recorded in either
b
DMSO-d6 or pyridine-d5 (*). nd ) peak not detected. Overlapping
multiplicity.
3
Compound 1 afforded molecular ions at m/z 614 [M +
+
+
H] and 636 [M + Na] in positive-ion ESI-MS. The odd
molecular weight of 613 implies the existence of an odd
number of nitrogen atom. Its akaloid nature is also evident
from its positive response against Dragendorff’s reagent. A
molecular formula of C35
ESI-MS (found 614.3696 [M + H] , calcd 614.3687),
H
51NO
8
for 1 was deduced by HR-
+
1
3
corresponding to 11 double-bond equivalence (DBE). Its IR
spectrum exhibited absorptions at 3405, 1631, and 1599 cm
Comparing the C NMR data with those of cimicifugoside
-1
4
H1 (Supporting Information), which was also isolated from
owing to to hydroxyl groups and double bond stretches. The
H NMR spectrum (Table 1) showed the signals due to a
typical cyclopropane methylene at δ 1.02 and 2.01 (each 1H,
d, J ) 3.4); seven tert-methyl groups at δ 1.06, 1.16, 1.35,
the same source, we conclude that 1 possesses a similar
1
structure to cimicifugoside H1 with respect to rings A, B,
1
13
and C. The H and C signals arising from the second portion
of the structure, however, differ profoundly from those of
cimicifugoside H1 and do not match signals from any other
structures reported thus far in the literature, suggesting a
novel strcuture of compound 1. Our efforts to make fine
crystals from 1 failed which precluded the possibility to
determine the structure directly by X-ray crystallography.
Therefore, the structure determination of 1 will be achieved
merely by interpretating of NMR spectroscopic data.
1.42, 1.51, 1.64 and 2.20 (each 3H, s); and an anomeric
2
5
(
3) Compound 1: white powder; mp 246-248 °C; [R] D +13 (c 0.095,
-1
MeOH); IR (KBr) νmax 3405, 2967, 1631, 1599, 1372, 1040, and 975 cm
H and C NMR data, see Table 1; ESIMS m/z (rel int) 614 [M + H]
;
1
13
+
+
+
(
100), 1249 [2M + Na] (34), 636 [M + Na] (16).
(
4) (a) Mamoru, K.; Yoshinobu, A.; Nobuko, S.; Masahiro, N. Chem.
Pharm. Bull. 1995, 43, 771-776. (b) Shigetoshi, Kadota, K.; Jian, X. L.;
Ken, T.; Tsuneo, N. Tetrahedron 1995, 51, 1143-1166.
1814
Org. Lett., Vol. 9, No. 9, 2007