Supporting Information
Two new triterpene saponins from the aerial parts of
Anemone taipaiensis
Hui Liab1, Xiao-Yang Wang c1, Xia-Yin Wang b, Dong Huab, Yang Liub and Hai-Feng
Tanga.b
a
Institute of Materia Medica, School of Pharmacy, Fourth Military Medical University, Xi’an 710032,
China; bShaanxi University of Chinese Medicine, Xi’an 712046, China; cDepartment of Pharmacy, 302
Hospital of Chinese PLA, Beijing 100039, China
* Corresponding author. E-mail addresses:tanghaifeng71@163.com (Hai-Feng Tang)
Identification data of compounds 36
Compound
3:
3β-O-{β-D-xylopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L
-arabinopyranosyl} oleanolic acid
22
White amorphous powder; m.p. 232−235 °C; [α] D +1.6 (c 0.13, MeOH); ESI-MS (pos.
ion mode) m/z 889 [M+Na]+; ESI-MS (neg. ion mode) m/z 865 [M−H]−. The presence
of
D-xylose, L-rhamnose
and L-arabinose in a ratio of 1:1:1 in compound 3 was
determined by GC analysis of the corresponding trimethylsilylated derivatives. 1H
NMR (500 MHz, pyridine-d5) δH 0.82, 0.94, 0.97, 0.99, 1.12 (each 3H, s, CH3), 1.29
(6H, s, 2 × CH3), 1.53 (3H, d, J = 6.0 Hz, CH3 of Rha), 3.26-3.28 (1H, m, H-3),
3.27-3.29 (1H, m, H-18), 4.84 (1H, d, J = 6.0 Hz, H-1 of Ara), 5.33 (1H, d, J = 7.6 Hz,
H-1 of Xyl), 5.45 (1H, br s, H-12) and 6.25 (1H, br s, H-1 of Rha); 13C NMR data, see
S.Table
1.
These
data
revealed
that
the
compound
3
was
3β-O-{β-D-xylopyranosyl-(1→3)-α-L -rhamnopyranosyl-(1→2) -α-L-arabinopyranosy
-l}oleanolic acid [1].
Compound 4: 3β-O-{α-L-rhamopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-Larabinopyranosyl} oleanolic acid
22
White amorphous powder; m.p. 244−247 °C; [α] D −6.2 (c 0.15, MeOH); ESI-MS (pos.
ion mode) m/z 919 [M+Na]+; ESI-MS (neg. ion mode) m/z 895 [M−H]−. The presence
of D-glucose, L-rhamnose and L-arabinose in a ratio of 1:1:1 in compound 4 was
determined by GC analysis of the corresponding trimethylsilylated derivatives. 1H
NMR (500 MHz, pyridine-d5) δH 0.81, 0.93, 0.96, 0.99, 1.08 1.16, 1.27 (each 3H, s,
CH3), 1.62 (3H, d, J = 6.2 Hz, CH3 of Rha), 3.23 (1H, dd, J = 4.4, 11.7 Hz, H-3), 3.27
2
(1H, dd, J = 4.0, 13.9 Hz, H-18), 4.75 (1H, d, J = 6.1 Hz, H-1 of Ara), 5.11 (1H, d, J
= 7.9 Hz, H-1 of Glc), 5.45 (1H, br s, H-12) and 6.16 (1H, br s, H-1 of Rha);
13
C
NMR data, see S.Table 1. These data revealed that the compound 4 was
3β-O-{α-L-rhamopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranoyl}
oleanolic acid [2].
Compound 5: kizutasaponin K12
22
White amorphous powder; [α] D −20.3 (c 2.73, MeOH); ESI-MS (pos. ion mode) m/z
1243 [M+Na]+; ESI-MS (neg. ion mode) m/z 1219 [M−H]−. The presence of D-glucose,
L-rhamnose
and L-arabinose in a ratio of 2:2:1 in compound 5 was determined by GC
analysis of the corresponding trimethylsilylated derivatives. 1H NMR (500 MHz,
pyridine-d5) δH 0.84, 0.85, 0.96, 1.05, 1.09 1.14 (each 3H, s, CH3), 1.62 (3H, d, J = 6.2
Hz, CH3 of Rha II), 1.67 (3H, d, J = 6.3 Hz, CH3 of Rha I), 3.15 (1H, dd, J = 3.8, 13.5
Hz, H-18), 4.97 (1H, d, J = 7.8 Hz, H-1 of Glc II), 5.07 (1H, d, J = 6.2 Hz, H-1 of
Ara), 5.37 (1H, br s, H-12), 5.84 (1H, br s, H-1 of Rha I), 6.21 (overlapped, H-1 of
Glc I) and 6.23 (1H, br s, H-1 of Rha II);
13
C NMR data, see S.Table 1. These data
revealed that the compound 5 was kizutasaponin K12 [3].
Compound 6: hederacolchiside E
22
White amorphous powder; m.p. 240−243°C; [α] D −19.6 (c 0.25 MeOH), ESI-MS
(pos. ion mode) m/z 1389 [M+Na]+; The presence of
L-arabinose
D-glucose, L-rhamnose
and
in a ratio of 3:2:1 in compound 6 was determined by GC analysis of the
corresponding trimethylsilylated derivatives. 1H NMR (500 MHz, pyridine-d5) δH 0.87
(6H, s, 2 × CH3), 0.86, 1.07, 1.09, 1.15, 1.22 (each 3H, s, CH3), 1.61 (3H, d, J = 6.1 Hz,
3
CH3 of 3-O-Rha), 1.68 (3H, d, J = 6.1 Hz, CH3 of 28-O-Rha), 3.15 (1H, dd, J = 4.0,
11.5 Hz, H-18), 3.18 (1H, dd, J = 3.6, 13.6 Hz, H-3), 4.75 (1H, d, J = 6.0 Hz, H-1 of
Ara), H-1 of 28-O-Glc II (overlapped), 5.12 (1H, d, J = 7.9 Hz, H-1 of 3-O-Glc), 5.39
(1H, br s, H-12), 5.84 (1H, s, H-1 of 28-O-Rha), 6.15 (1H, s, H-1 of 3-O-Rha) and 6.22
(1H, d, J = 8.2 Hz, H-1 of 28-O-Glc I);
13
C NMR data, see S.Table 1. These data
revealed that the compound 6 was hederacolchiside E [4].
GC analysis after acid hydrolysis of 3−6 with the same method as 1 and 2.
References
[1] K. Nakayama, H. Fujino , R. Kasai, O. Tanaka, and J. Zhou, Chem. Pharm. Bull. 34, 2209
(1986).
[2] Y. Mimaki, M. Kuroda, T. Asano, and Y. Sashida, J. Nat. Prod. 62, 1279 (1999).
[3] H. Kizu, H. Shimana, and T. Tomimori, Chem. Pharm. Bull. 43, 2187 (1995).
[4] X. Liao, Y.Z. Chen, L.S. Ding, and B.G. Li, Nat. Prod. Res. Dev. 6, 342 (1999).
4
S.Table 1 13C NMR (125 MHz) chemical shifts of compounds 3~6 in pyridine-d5
C
1
2
3
4
5
6
7
8
9
10
11
12
13
3
38.9
26.5
88.6
39.4
55.8
18.4
33.2
39.6
48.1
37.1
23.8
122.5
144.8
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
42.0
28.4
23.6
46.8
41.9
46.4
30.8
34.0
33.3
28.2
17.0
15.4
17.3
26.1
180.3
33.1
23.6
4
38.8
26.5
88.6
39.3
55.9
18.5
33.1
39.7
48.0
36.9
23.7
122.3
144.7
42.1
28.3
23.6
46.8
41.8
46.1
5
38.9
26.2
81.8
43.5
47.5
18.2
32.9
39.8
48.1
36.9
23.7
122.8
144.1
42.0
28.2
23.2
46.9
41.7
46.2
30.8
34.1
33.2
63.8
14.0
16.0
17.4
26.1
180.2
33.2
23.6
30.8
34.0
32.4
63.9
13.9
16.0
17.4
26.0
176.4
33.2
23.6
6
38.9
26.5
88.6
39.4
55.8
18.4
33.2
39.7
48.1
37.1
23.8
122.7
144.2
42.0
28.3
23.4
46.9
41.5
46.4
30.8
34.0
33.4
28.1
17.0
15.4
17.3
26.1
176.5
33.1
23.6
3-O-sugar
Ara-1
2
3
4
5
Rha-1
2
3
4
5
6
Xyl-1
2
3
4
5
Glc-1
2
3
4
5
6
28-O-sugar
GlcI-1
2
3
4
5
6
GlcII-1
2
3
4
5
6
Rha-1
2
3
4
5
6
5
3
4
5
6
105.1
75.3
74.5
69.2
65.4
101.6
72.1
72.3
74.0
69.5
18.5
107.5
75.5
78.2
71.2
67.5
104.9
76.2
75.0
80.4
65.4
101.6
72.2
72.4
74.1
69.6
18.6
104.2
75.8
74.9
69.5
65.7
101.6
72.3
72.6
74.2
69.7
18.6
104.8
76.2
74.3
79.6
64.5
101.6
72.2
72.4
74.1
69.7
18.5
106.2
75.3
78.5
71.2
78.6
62.4
106.3
75.6
78.6
71.0
78.6
62.5
95.6
73.7
78.6
70.7
78.1
69.1
104.7
75.2
76.4
78.3
77.2
61.2
102.6
72.5
72.6
74.1
70.3
18.4
95.5
73.8
78.7
70.8
78.0
69.2
104.9
75.3
76.5
78.2
77.3
61.1
102.7
72.5
72.7
74.0
70.2
18.5