Terpenoid indole alkaloids from Mappianthus iodoides Hand.-Mazz.

Article abstract of DOI:10.1016/j.phytochem.2014.01.004

Ten terpenoid indole alkaloids, mappiodines A-C and mappiodosides A-G, together with eight known compounds, were isolated from stems of Mappianthus iodoides Hand.-Mazz. Their structures were elucidated by spectroscopic analyses including 1D, 2D NMR, MS and CD methods. The ten compounds were evaluated for their cytotoxic activity, but were inactive.

Full text of DOI:10.1016/j.phytochem.2014.01.004

Phytochemistry 100 (2014) 76–85
Contents lists available at ScienceDirect
Phytochemistry
journal homepage: www.elsevier.com/locate/phytochem
Terpenoid indole alkaloids from Mappianthus iodoides Hand.-Mazz.
⇑
Hai-Jian Cong, Qing Zhao, Shu-Wei Zhang, Jiao-Jiao Wei, Wen-Qiong Wang, Li-Jiang Xuan
State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Zhangjiang Hi-Tech Park, Shanghai 201203, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Ten terpenoid indole alkaloids, mappiodines A–C and mappiodosides A–G, together with eight known
compounds, were isolated from stems of Mappianthus iodoides Hand.-Mazz. Their structures were eluci-
dated by spectroscopic analyses including 1D, 2D NMR, MS and CD methods. The ten compounds were
evaluated for their cytotoxic activity, but were inactive.
Received 6 December 2012
Received in revised form 25 July 2013
Available online 1 February 2014
Ó 2014 Elsevier Ltd. All rights reserved.
Keywords:
Mappianthus iodoides
Icacinaceae
Terpenoid indole alkaloid
Introduction
comparison with data in the literature. A biogenetic pathway for
the indole alkaloids is proposed.
The genus Mappianthus (Icacinaceae family) consists of three
species which are distributed in subtropical and tropical zones.
Mappianthus iodoides Hand.-Mazz., one species occurring in China,
is used by local people for treatment of conditions including trau-
matic injury, rheumatalgia and arthralgia (Fang and Qin, 2002).
Phytochemical studies have led to isolation of monoterpenoid in-
dole alkaloids, sesquiterpenes, iridoid glycosides, lignans and phe-
nolic glycosides (Chen et al., 2000; Xiao et al., 2011). These
monoterpenoid indole alkaloids originate from condensation of
tryptophan with secologanin to give strictosidine, which then elab-
orates to an impressive array of structural variants (Hutchinson,
1981). Many of them, such as yohimbine (Bader et al., 1954),
reserpine (Muller et al., 1952), and camptothecin (Mattern et al.,
1987; Jain et al., 1998), are well known for their pharmacological
significance. This study of M. iodoides focused on indole alkaloids,
and led to the isolation of ten previously unreported monoterpe-
noid indole alkaloids, namely, mappiodines A–C (1–3), mappiodo-
sides A–G (4–10), and eight known alkaloids. The structures of
the ten alkaloids were elucidated by spectroscopic methods, while
the known alkaloids were identified as tryptophan (Bak et al.,
1968), 1-methyl-1,2,3,4-tetrahydro-b-carboline-3-carboxylic acid
(Kicha et al., 2003), 5-carboxystrictosidine (Aimi et al., 1992),
Results and discussion
Mappiodine A (1) was obtained as a yellow amorphous powder
and had a molecular formula of C22H28N2O6 by HRESIMS. Its IR
spectrum showed bands at 1724 and 1628 cmꢀ1 due to the pres-
ence of carbonyl groups, while the UV spectrum had absorption
maxima at 206, 274 and 311 nm, suggesting the presence of an in-
dole chromophore group. The 1H NMR and 13C NMR spectroscopic
data of 1 indicated presence of a 1,2,4-trisubstituted phenyl ring
[dH 7.50 (d, J = 2.1 Hz), 7.42 (d, J = 8.5 Hz) and 7.24 (dd, J = 8.5,
2.1 Hz)] (Table 2), one tetrasubstituted double bond (dC 136.7
and 105.9), two carbonyl groups (dC 176.4 and 175.6), two methyls,
five methylenes and five methines, respectively (Table 1). In the
1H–1H COSY spectrum, correlations between H-3/H-14/H-15/H-
16/H-17, H-18/H-19/H-20/H-21, H-15/H-20, H-5/H-6 and H-11/
H-12 were apparent. The 13C and 1H NMR spectroscopic data of 1
were very similar to those of dihydrositsirikine (Clivio et al.,
1991), except for additional signals for one carboxyl group and
one hydroxyl group. The carboxyl group was located at C-5 as de-
duced from the HMBC correlation between H-5 (dH 3.73) and C-23
(dC 176.4). The methoxyl group was considered to be bound to
C-22 by a HMBC correlation between the OMe (dH 3.50) and C-22
strictosidinic acid (Subhadhirasakul et al., 1994), 3
a
, 5
, 5
a
a
-tetrahy-
-tetrahy-
drodeoxycordifoline lactam (Lamidi et al., 2005), 3
a
(dC 175.6) functionalities. The H-15 is almost invariably a-oriented
in the skeleton of these alkaloids (Brown et al., 1972), according to
the biogenetic pathway (Fig. 5). The coupling constants
drodeoxycordifolic acid (De Silva et al., 1971), lyaloside (Valverde
et al., 1999), and desoxycordifoline (Brandt et al., 1999) by
(J3, 14b = 10.6 Hz, J 14b, 15 = 12.0 Hz) suggested
relationship for H-3/H-14b/H-15. ROESY correlations of H-3/H-5,
H-3/H-15, H-3/H-20 and H-15/H-20 indicated an -orientation of
a trans-diaxial
⇑
Corresponding author. Tel./fax: +86 21 20231968.
E-mail address: ljxuan@mail.shcnc.ac.cn (L.-J. Xuan).
a
0031-9422/$ - see front matter Ó 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.phytochem.2014.01.004

H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
77
Table 1
13C NMR Spectroscopic Data (125 MHz) for Compounds 1–10.a
No.
1b
2c
3d
4b
5c
6d
7d
8e
9e
10c
2
3
5
6
7
8
9
136.7, s
61.2, d
67.3, d
27.9, t
105.9, s
129.1, s
103.7, d
152.8, s
112.3, d
112.6, d
132.7, s
33.3, t
41.7, d
49.7, d
59.3, t
10.9, q
23.9, t
134.9, s
140.9, s
132.8, d
116.6, d
131.9, s
121.5, s
106.6, d
152.4, s
123.2, d
114.7, d
139.6, s
29.8, t
130.1, s
61.9, d
68.5, d
26.1, t
105.9, s
128.0, s
103.3, d
152.0, s
113.3, d
113.1, d
133.1, s
32.5, t
31.4, d
109.8, s
157.3, d
18.6, q
71.9, d
38.7, d
53.3, t
137.0, s
61.1, d
67.1, d
27.8, t
106.5, s
128.5, s
106.5, d
153.2, s
113.6, d
112.3, d
134.2, s
33.3, t
41.7, d
49.6, d
59.2, t
10.9, q
23.9, t
135.5, s
141.9, s
133.4, d
116.9, d
132.8, s
121.6, s
109.4, d
154.4, s
125.3, d
114.7, d
141.4, s
30.1, t
130.7, s
61.8, d
68.4, d
26.1, t
106.8, s
127.6, s
106.0, d
153.5, s
114.9, d
113.0, d
134.5, s
32.6, t
31.5, d
109.8, s
157.3, d
18.6, q
72.0, d
38.7, d
53.4, t
178.2, s
65.5, d
59.3, d
39.1, t
177.4, s
62.6, d
57.6, d
38.5, t
135.2, s
53.4, d
63.0, d
26.6, t
108.1, s
127.2, s
104.6, d
151.3, s
112.6, d
111.6, d
132.1, s
27.0, t
131.4, s
53.0, d
59.3, d
23.8, t
108.1, s
127.7, s
106.4, d
153.2, s
114.8, d
112.8, d
134.6, s
34.4, t
32.5, d
108.5, s
157.4, d
120.1, t
135.0, d
45.2, d
97.5, d
171.9, s
53.1, q
175.5, s
100.4, d
74.5, d
77.8, d
71.4, d
78.8, d
62.5, t
58.7, s
56.6, s
130.8, s
124.6, d
123.8, d
130.8, d
111.7, d
142.6, s
26.9, t
27.9, d
108.4, s
149.2, d
120.5, t
133.3, d
44.5, d
97.6, d
165.9, s
129.8, s
125.9, d
121.5, d
128.3, d
109.9, d
141.6, s
25.0, t
23.1, d
108.4, s
146.1, d
120.1, t
132.5, d
43.3, d
94.6, d
166.0, s
10
11
12
13
14
15
16
17
18
19
20
21
22
OMe
23
10
27.6, d
28.0, d
29.6, d
95.8, s
112.7, s
154.3, d
18.5, q
71.8, d
36.8, d
111.2, s
155.7, d
18.6, q
72.1, d
37.1, d
146.5, d
118.6, t
134.5, d
40.0, d
71.5, t
39.9, d
58.1, t
175.6, s
51.7, q
176.4, s
39.9, d
58.0, t
55.6, t
174.0, s
55.8, t
172.5, s
170.4, s
175.5, s
51.7, q
176.6, s
104.9, d
75.6, d
78.9, d
71.7, d
79. 1, d
62.7, t
170.4, s
165.0, s
174.1, s
174.1, s
103.7, d
75.1, d
77.9, d
71.6, d
78.0, d
62.6, t
174.8, s
99.8, d
74.6, d
77.8, d
71.5, d
78.3, d
62.6, t
172.8, s
97.7, d
73.1, d
76.4, d
70.0, d
77.4, d
61.0, t
172.5, s
102.1, d
75.4, d
78.7, d
71.7, d
79.4, d
61.0, t
103.3, d
74.9, d
77.8, d
71.4, d
78.2, d
62.6, t
20
30
40
50
60
100
200
300
400
500
600
103.7, d
75.0, d
77.9, d
71.6, d
78.5, d
62.9, t
a
b
c
Values in d (ppm).
Spectra obtained in pyridine-d5.
Spectra obtained in CD3OD + D2O.
Spectra obtained in CD3OD.
d
e
Spectra obtained in DMSO-d6.
Table 2
1H NMR Spectroscopic Data (500 MHz) for Compounds 1–5.a
No.
1b
2c
3d
4b
5c
1
11.69, s
11.89, s
3
5
6
9
11
12
14
14b
15
16
17
18
19
20
3.60, d (10.6)
3.73, dd (10.4, 2.9)
3.34, m; 3.63, m
7.50, d (2.1)
7.24, dd (8.5, 2.1)
7.42, d (8.5)
2.74, d (12.2)
2.01, ddd (12.2, 12.0, 10.6)
2.11, m
3.28, m
4.02, dd (10.6, 3.8) 4.33, m
0.81, t (7.3)
1.25, m; 1.60, m
2.05, m
4.17, d (10.9)
3.69, m
3.58, d (10.7)
8.24, d (6.6)
8.22, d(6.6)
7.50, d (2.1)
7.28, dd (8.9, 2.1)
7.53, d (8.9)
3.96, dd (17.5, 6.2)
3.25, dd (17.5, 8.6)
3.13, dd (14.6, 6.5)
4.01, dd (10.6, 3.9)
3.30, m; 3.53, m
7.75, d (2.1)
7.41, dd (8.6, 2.1)
7.37, d (8.6)
2.73, d (12.0)
2.00, ddd (12.0, 11.5, 10.7)
2.11, m
3.27, m
4.01, dd (10.6, 3.9) 4.33, m
0.79, t (7.4)
1.23, m; 1.59, m
2.04, m
8.39, d (5.6)
8.47, d (5.6)
7.96, s
7.57, m
7.65, m
4.08, m
3.25, m
3.09, m
3.08, m; 3.27, m
6.79, d (2.0)
6.71, dd (8.7, 2.0)
7.18, d (8.7)
2.93, d (14.2)
a
1.71, ddd (14.2, 11.4, 10.9)
2.87, d (11.4)
7.52, s
1.44, d (6.2)
3.88, dq (9.1, 6.2)
2.54, m
7.62, s
7.63, s
1.49, d (5.6)
4.45, dq (10.1, 5.6)
1.93, m
1.47, d (6.0)
3.95, m
2.54, m
5.01, m
4.61, m
21
a
3.80, dd (10.2, 2.1)
2.25, t (10.2)
3.50, s
4.92, dd (14.4, 5.1)
4.57, dd (14.4, 4.3)
4.09, d (12.5)
3.10, m
3.78, dd (10.5, 2.1)
2.24, t (10.5)
3.48, s
5.72, d (6.9)
4.40, m
4.13, m
4.42, m
4.44, m
4.46, m
21b
OMe
10
5.11, d (6.9)
3.55, m
3.55, m
3.44, m
3.59, m
20
30
40
50
60
4.00, d (12.0)
3.76, dd (12.0, 6.2)
4.56, dd (11.8, 1.9)
a
b
c
Values in d (ppm); coupling constants (Hz) in parentheses.
Spectra obtained in pyridine-d5.
Spectra obtained in CD3OD + D2O.
d
Spectra obtained in CD3OD.

78
H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
23
COOH
COOH
N
6
5
18
H
18
RO
N+
21
9
7
RO
N
3
8
H
RO
2
10
11
19
OH
19
20
O
15
N
H
N
O
13
H
14
H
N
H
17
16
H
12
H
17
16
COO-
H
22
H3COOC
HOOC
22
2 R = H
1 R = H
3 R = H
5
R = Glc
4
6
R = Glc
R = Glc
OH
23
COOH
O
HO
HO
17
N
O
O
16
15
20
19
OH
22
COOH
COOH
O
5
N
H
H
14
O
O
6
H
21
N
N
H
3
9
16
7
2
17
HO
O
15
18
COOH
H
N
H
H
N
H
O
1"
O
14
O
21
O
H
O
H
HO
HO
20
H
H
OH
O
19
O
1'
OH
NH
H
18
COOCH3
O
N
O
OH
H
H
O
HO
HO
H
O
1'
OH
HO
OH
HO
OH
O
10
7
8
HO
HO
OH
Fig. 1. Chemical structures of compounds 1–10.
H-3, H-5, and H-20 (Fig. 3). Thus, mappiodine A (1) was established
as shown (Fig. 1).
HRESIMS. Its IR spectrum had an absorption band at 1630 cmꢀ1
due to presence of an , b-unsaturated carbonyl group, and its
a
Mappiodine B (2), isolated as a yellow amorphous powder, had
to a molecular formula of C20H18N2O4 by HRESIMS. Its IR spectrum
UV spectrum had absorption maxima at 224 and 275 nm, consis-
tent with an indole chromophore. Analysis of the 1H NMR and
13C NMR spectra of 3 established a 1,2,4-trisubstituted phenyl ring
[dH 7.18 (d, J = 8.7 Hz), 6.79 (d, J = 2.0 Hz) and 6.71 (dd, J = 8.7,
2.0 Hz)], a trisubstituted double bond [(dH 7.62, dC 157.3) and dC
109.8)], a tetrasubstituted double bond, one methyl group, three
methylene groups, five methine groups and two carboxyl groups,
respectively (Tables 1 and 2). In the 1H–1H COSY spectrum, corre-
lations between H-18/H-19/H-20/H-21, H-3/H-14/H-15/H-20, H-5/
H-6 and H-11/H-12 were apparent. These characteristics suggested
that 3 possessed a carbon skeleton similar to that of aricine (Iac-
obucci and Deulofeu, 1957). However, a key difference between
these two compounds was that 3 possessed one more carboxyl
group. The carboxyl group (dC 174.1) was deduced to be bound
to C-5 by the HMBC correlation between H-5 (dH 3.69) and C-23
showed bands at 1675 and 1637 cmꢀ1 due to the presence of an
a,
b-unsaturated carbonyl group, and its UV spectrum had absorption
maxima at 210, 233, 273 and 314 nm, indicating the presence of an
indole chromophore and an a, b-unsaturated carbonyl moiety. In
the 1H NMR spectrum, compound 2 had signals corresponding to
a 1,2,4-trisubstituted phenyl ring at dH 7.53 (d, J = 8.9 Hz), 7.50
(d, J = 2.1 Hz) and 7.28 (dd, J = 8.9, 2.1 Hz), a tetrasubstituted pyri-
dine ring at dH 8.24 (d, J = 6.6 Hz) and 8.22 (d, J = 6.6 Hz), and an
olefinic proton at dH 7.52 (s, 1H), respectively (Table 2). The 13C
NMR and DEPT spectra also indicated the existence of one carbonyl
group (dC 174.0), six aromatic carbons (dC 152.4, 139.6, 123.2,
121.5, 114.7, 106.6), five pyridine carbons (dC 140.9, 134.9, 132.8,
131.9, 116.6) and one trisubstituted double bond (dC 154.3,
112.7) (Table 1). Analysis of the 1D and 2D NMR spectra showed
that 2 was similar to rauvotetraphylline E (Gao et al., 2012), a
known monoterpenoid indole alkaloid isolated from Rauwolfia tet-
raphylla, except for the existence of a hydroxyl group in 2. The ste-
reochemistry of 2 was determined through analysis of all proton
coupling constants and from ROESY correlations. The coupling con-
(dC 174.1). The coupling constants (J 3, 14b = 10.9 Hz, J 14b,
=
15
11.4 Hz and J
20 = 10.1 Hz) suggested a trans relationship of
19,
H-3/H-14b/H-15, H-19/H-20, and ROESY correlations of H-3/H-5,
H-3/H-15 and H-15/H-20 indicated that H-3, H-5, H-15 and H-20
were
a-oriented (Fig. 3). ROESY correlations of H-19/H-14b and
H-3/H-14
a
established that H-19 was b-oriented. Thus, the relative
stants (J
, 15 = 6.2 Hz, J 14b, 15 = 8.6 Hz, J 19, 20 = 9.1 Hz) strongly
configuration of 3 was determined.
14
a
suggested a trans-diaxial relationship of H-14b/H-15 and H-19/
H-20. Combined with the ROESY correlations of H-14b/H-21b,
H-14b/H-19, H-14a/H-15, H-15/H-20 and H-19/H-21b, its relative
configuration could be determined (Fig. 3). Accordingly, 2 was as-
signed an inner salt form (Xiao et al., 2011) and named mappiodine
B.
Mappiodoside A (4), a yellow amorphous powder, was deter-
mined to have molecular formula of C28H38N2O11 by HRESIMS. Its
IR spectrum had similar bands to those of 1, and its UV spectrum
(209, 270 and 311 nm) was also similar to 1. By comparison of
the 1H and 13C NMR spectroscopic data with those of 1, compound
4 differed in resonances corresponding to one additional sugar
Mappiodine C (3) was obtained as a yellow amorphous powder
and its molecular formula was determined to be C21H22N2O6 by
unit. Cellulase hydrolysis of 4 produced compound 1 and
cose. Its sugar unit was identified as b-glucose from the proton
D-glu-

H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
79
COOH
N
COOH
N
HO
N+
HO
HO
OH
O
N
H
O
N
H
N
H
-OOC
H3COOC
HOOC
N+
3
1
2
OH
OH
COOH
N
O
HO
HO
O
O
HO
HO
O
OH
OH
O
N
H
OH
N
H
-OOC
COOH
H3COOC
5
4
COOH
O
N
O
N
OH
COOH
N
N
H
O
O
O
HO
HO
N
H
O
O
O
O
OH
O
O
O
N
H
HO
HO
O
O
OH
HO
HO
OH
HOOC
HO
HO
6
8
7
HO
O
HO
HO
COOH
OH
NH
OH
COOCH3
COOH
N
N
H
O
HO
HO
O
O
O
O
OH
O
N
H
O
OH
HO
HO
OH
10
9
Fig. 2. Key HMBC (H ? C) and 1H-1H COSY (-) correlations of 1–10.
at dH 5.72 (d, J = 6.9 Hz) and the anomeric carbon at 104.9. The
Mappiodoside C (6), a yellow amorphous powder, was deter-
mined to have the molecular formula of C27H32N2O11 by HRESIMS.
By comparison of the 1H and 13C NMR spectroscopic data with
those of 3, compound 6 had the same moiety as 3, except for res-
onances of one additional sugar unit. The sugar unit was identified
as b-glucose from the proton at dH 4.83 (d, J = 7.3 Hz) and the ano-
meric carbon at dC 103.7. This was confirmed by cellulase hydroly-
b-D-glucose unit was deduced to be located at C-10 due to the
HMBC correlation between H-10 (dH 5.72) and C-10 (dC 153.2).
Thus, compound 4 had the same stereochemistry as compound 1,
which was also confirmed by the ROESY spectrum of 4. Thus, com-
pound 4 was named mappiodine A 10-O-b-D-glucoside.
Mappiodoside B (5), a yellow amorphous powder, had a molec-
ular formula of C26H28N2O9 by HRESIMS. Its IR and UV spectra were
similar to those of 2. By comparison of the 1H and 13C NMR spec-
troscopic data with those of 2, compound 5 was had the same moi-
ety as 2, except for resonances of one additional sugar unit. The
latter was identified as b-glucose from the proton at dH 5.11 (d,
J = 6.9 Hz) and the anomeric carbon at dC 103.3. This was confirmed
sis of 6, which yielded D-glucose and compound 3. The b-D-glucose
unit was located at C-10 due to the HMBC correlation between H-10
(dH 4.83) and C-10 (dC 153.5). The relative configuration was fur-
ther confirmed by the ROESY spectrum. Compound 6 was named
mappiodine C 10-O-b-D-glucoside.
Mappiodoside D (7) was obtained as a colorless amorphous
powder. It had a molecular formula of C27H30N2O11 as determined
from the HRESIMS, 1H NMR and 13C NMR spectroscopic data. In its
1H NMR spectrum, compound 7 displayed signals corresponding to
a 1, 2-disubstituted phenyl ring at dH 7.26 (dd, J = 7.4, 7.4 Hz), 7.03
(dd, J = 7.4, 7.4 Hz), 6.96 (d, J = 7.4 Hz) and 6.90 (d, J = 7.4 Hz). Also
present were resonances assigned to a terminal vinyl group at dH
by cellulase hydrolysis of 5, which yielded
D
-glucose and com-
pound 2. The b-
D
-glucose moiety was located at C-10 is deduced
from the HMBC correlation between H-10 at dH 5.11 and C-10 at
dC 154.4. Its relative configuration was further confirmed by anal-
ysis of the ROESY spectrum. Compound 5 was named mappiodine
B 10-O-b-D-glucoside.

80
H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
H
H
N+
COOH
H
H
HO
H
HO
N
H
O
N
H
OH
N
H
H
H
H
H
H
COO-
H3COOC
2
1
GlcO
H
COOH
COOH
N
H
H
NH
H
HO
COOCH3
H
O
N
H
H
H
N
O
H
H
H
H
COOCH3
H
OGlc
10
3
8
9
7
Fig. 3. Key ROESY correlations of 1–3 and 7–10.
corresponding to each proton signal was achieved by analysis of
an HSQC experiment. Its 1H–1H COSY spectrum indicated four sep-
arate spin–spin coupling systems. In the 13C NMR spectrum, a sp3
quaternary carbon at dC 58.7 (C-7) and a carbonyl carbon at dC
178.2 (C-2) suggested the presence of an oxindole ring which
was linked to a pyrrole ring via spiro-carbon C-7 (Pham et al.,
2005). This was supported by analysis of the HMBC spectrum, in
which long range correlations were observed from both H-3 (dH
4.24) and H2-6 (dH 2.43) to C-2 (dC 178.2), from H-3 (dH 4.24),
H2-6 (dH 2.43) and H-9 (dH 6.90) to C-7 (dC 58.7), and from H2-6
(dH 2.43) to C-3 (dC 65.5) (Fig. 2). The carboxyl group (dC 174.8)
was indicated to be bound to C-5 by the HMBC correlation between
the H-5 (dH 4.84) and C-23 (dC 174.8). These findings showed that 7
was closely related to javaniside, a known monoterpenoid 2-oxo-
indole alkaloid previously isolated from an Alangium species (Pham
et al., 2005), except for the existence of a carboxyl group at C-5.
The stereochemistry of 7 was determined through careful anal-
ysis of all proton coupling constants and ROESY correlations. The
coupling constants between H-20/H-21 (J = 1.7 Hz) and H-20/H-
Fig. 4. CD spectra of compounds 7 and 8.
5.27 (dt, J = 17.2, 10.1 Hz), 5.06 (dd, J = 17.2, 1.6 Hz) and 4.96 (dd,
J = 10.1, 1.6 Hz), an olefinic proton at d 7.40 (d, J = 2.1 Hz), and a
hemi-acetal proton at dH 5.41 (d, J = 1.7 Hz) (Table 3). The 13C
and DEPT spectra established the presence of three carbonyl
groups (dC 178.2, 174.8 and 165.9), six aromatic carbons (dC
142.6, 130.8, 130.8, 124.6, 123.8 and 111.7), two aliphatic terminal
vinyl carbons (dC 133.3 and 120.5), and one trisubstituted double
bond (dC 149.2 and 108.4) (Table 1). Additionally, signals
corresponding to a glucopyranose moiety were also identified from
13C NMR experiments. The assignment of carbon resonances
15 (J = 5.6 Hz) strongly suggested the b/b/
H-20, H-21. The b configuration of H-3 was supported by coupling
constants between H-3 and H-14 protons (J = 11.4 Hz, J
3,14b = 3.4 Hz). Combined with ROESY correlations of H-9/H-14a,
H-9/H-5, the relative configuration could be determined (Fig. 3).
Its CD spectrum exhibited a positive Cotton effect at 285 nm
(De = +2.89, Fig. 4), indicating that the absolute configuration at
C-7 was R (Ali et al., 1975; Aimi et al., 1997). Accordingly, 3R, 5S,
7R, 15S, 20R and 21S configurations were readily assigned based
on the relative configurations.
a orientation of H-15,
3,14a

H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
81
COOH
COOH
H
OGlc
7
N
R1
H
OGlc
O
NH2
+
OHC
R1
2
O
N
H
N
H
H
H
R2OOC
R2OOC
secologanin R2 = Me
L-tryptohan
R1 = H
COOH
NH
COOH
COOH
COOH
H
OGlc
O
R1
H
OGlc
O
NH
H
H
N
N
R1
H
OGlc
O
H
OGlc
O
N
H
H
N
H
H
N
H
N
H
H
R2OOC
5-carbosystrictosidine
R1 = H R2 = Me
HOOC
H
H
R2OOC
COOH
ROOC
COOH
N+
COOH
COOH
NH
-Glc
C15-C16
rotation
OHC
NH
COOH
H
R1
R1
NH
H
H
R1
CHO
OH
OH
OH
H
N
H
H
O
N
N
H
H
α
15
H
N
H
H
H
H
R2OOC
R2OOC
OGlc
R2OOC
COOH
C14-C15 rotation
COOH
N+
R1
COOH
COOH
N
R1
OHC
NH
O
OH
H
R1
N
H
O
N
H
H
COOR2
CHO
N
H
H
H
β
15
R2OOC
NADPH
COOH
N
H
H
R2OOC
H
N
H
O
H
NADPH
COOH
OGlc
COOH
N+
N
H
R1
H
N
R1
R1
COOR2
CHO
COOH
OH
α
H
N
H
15
O
H
N
H
N
H
O
H
H
H
H
N
R2OOC
H
R2OOC
3 R1 = OH R2 = Me
R1 = OGlc R2 = Me
1 R1 = OH R2 = Me
4
R1 = OGlc R2 = Me
N
H
O
O
6
H
NADPH
COOH
OGlc
-COOH
7
8
and
COOH
N
N
R1
O
O
COOH
OH
R1
H
R
N+
N
H
H
H
β
15
N
H
H
O
H
N
H
H
H
H
-OOC
2
R1 = OH
5 R1 = OGlc
9 R1 = OGlc
Fig. 5. Postulated biogenetic pathway for compounds 1–9.
Mappiodoside E (8), a colorless amorphous powder, had the
same molecular formula as 7 on the basis of HRESIMS and NMR
spectra. The UV, IR, 1H NMR, and 13C NMR spectroscopic data were
similar to those of 7. Thus, 8 was considered to possess the same
skeletal structure as 7, and 2D NMR (1H–1H COSY, HSQC and
HMBC) confirmed this conclusion. The relative configuration of 8
was determined by the proton coupling constants and ROESY
correlations. The coupling constants between H-20/H-21
Mappiodoside F (9), a yellow amorphous powder, had a molec-
ular formula of C27H30N2O10 by HRESIMS. Its 1H NMR and 13C NMR
spectra indicated a 1,2,4-trisubstituted phenyl ring [dH 7.21 (d,
J = 8.7 Hz), 7.05 (d, J = 2.0 Hz) and 6.81 (dd, J = 8.7, 2.0 Hz)], one tri-
substituted double bond (dC 146.5 and 95.8), one tetrasubstituted
double bond (dC 135.2 and 108.1), two carbonyl groups (dC 172.5
and 165.0), three methylenes, four methines and a sugar unit (dC
102.1, 79.4, 78.7, 75.4, 71.7, 61.0), respectively (Tables 1 and 3).
Correlations between H-3/H-14/H-15/H-20/H-21, H-18/H-19/H-
20, H-5/H-6 and H-11/H-12 were apparent in the 1H–1H COSY
spectrum. Analysis of the 1D and 2D NMR spectra showed that
(J = 1.1 Hz) and H-20/H-15 (J = 5.3 Hz) strongly suggested a b/b/
orientation for H-15, H-20, H-21. Combined with the ROESY
correlations of H-9/H-14b, H-9/H-6b, H-5/H-6 , H-5/H-3, the rela-
tive configuration could be determined (Fig. 3). The CD spectrum
exhibited a negative Cotton effect at 283 nm (
a
a
compound 9 had a similar skeleton to that of 3a, 5a-tetrahydrode-
D
e
= ꢀ2.84, Fig. 4),
oxycordifoline lactam (Lamidi et al., 2005), except for a different
arrangement at the trisubstituted double bond and the carboxyl
group. This was validated by HMBC correlations between H-17/
suggesting that the absolute configuration at C-7 was S (Ali et al.,
1975; Aimi et al., 1997). Accordingly, 3S, 5S, 7S, 15S, 20R and 21S
configurations were readily assigned based on the relative
configurations.
C-5, H-17/C-3 and H-21/C-22. The
D-glucose, the presence of which
was confirmed by hydrolysis of 9, was located at C-10 by the HMBC

82
H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
Table 3
1H NMR Spectroscopic Data (500 MHz) for Compounds 6–10.a
No.
6b
7b
8c
9c
10d
3
5
4.04, d (11.5)
3.63, m
3.10, m
3.28, m
7.13, d (1.9)
4.24, dd (11.4, 3.4)
4.84, m
2.43, m
2.43, m
6.90, d, (7.4)
3.69, m
4.56, d (10.3)
2.72, t (12.3)
2.08, d (12.6)
4.86, m
4.47, m
3.78, m
3.30, m
2.95, m
4.16, d (8.7)
2.97, d (14.3)
2.71, m
6a
6b
9
7.56, d (7.5)
7.05, d (2.0)
7.13, d (1.9)
10
11
12
14
14b
15
7.03, dd, (7.4, 7.4)
7.26, dd, (7.4, 7.4)
6.96, d (7.4)
0.88, td (12.7, 11.4)
1.43, dd (12.7, 3.4)
3.12, m
6.95, dd(7.5, 7.5)
7.21, dd (7.5, 7.5)
6.88, d (7.5)
1.17, d (11.8)
1.58, td (11.8, 13.1)
3.10, m
6.99, dd (8.7, 1.9)
7.27, d (8.7)
2.91, d (14.0)
1.70, ddd (14.0, 11.5, 9.6)
2.85, m
6.81, dd (8.7, 2.0)
7.21, d (8.7)
1.73, m
2.53, m
2.45, m
6.96, dd (8.7, 1.9)
7.17, d (8.7)
2.23, m
2.38, m
3.05, m
a
17
7.62, s
7.40, d (2.1)
7.09, d (2.5)
7.70, s
7.85, s
18
1.50, d (6.1)
4.96, dd (10.1, 1.6)
5.06, dd (17.2, 1.6)
5.27, dt (17.2, 10.1)
2.55, ddd (9.5, 5.6, 1.7)
5.41, d (1.7)
5.13, dd (10.1, 1.7)
5.22, dd (17.2, 1.7)
5.56, dt (17.2, 10.1)
2.39, ddd (9.5, 5.3, 1.1)
5.29, d (1.1)
5.24, d (11.8)
5.28, d (18.4)
5.76, m
2.44, m
4.03, d (10.4)
4.26, d (10.4)
5.27, d (10.6)
5.38, d (17.2)
5.82, m
2.77, m
5.89, d (9.1)
19
20
21
4.46, dq (10.2, 6.1)
1.96, m
4.08, m
3.08, m
OMe
10
3.81, s
4.89, d (7.7)
3.26, m
3.46, m
3.27, m
3.53, m
3.73, m
3.93, d (11.7)
4.91, d (7.2)
3.26, m
3.52, m
3.27, m
3.53, m
3.68, m;
4.01, d (11.7)
4.83, d (7.3)
3.46, m
3.48, m
3.38, m
3.40, m
4.63, d (7.9)
3.18, m
3.36, m
3.25, m
3.27, m
4.48, d (7.8)
2.92, t (8.4)
2.99, t (9.2)
3.13, m
3.13, m
3.39, dd (11.6, 6.2)
3.65, m
4.75, d (7.4)
3.20, m
3.26, m
3.13, m
3.14, m
20
30
40
50
60
3.89, d (11.9)
3.69, dd (11.9, 5.0)
3.63, dd (11.9, 5.6)
3.86, dd (11.9, 1.8)
3.45, dd (11.5, 5.8)
3.67, d (11.5)
100
200
300
400
500
600
a
b
c
Values in d (ppm); coupling constants (Hz) in parentheses.
Spectra obtained in CD3OD.
Spectra obtained in DMSO-d6.
d
Spectra obtained in CD3OD + D2O.
correlation between H-10 (dH 4.75) and C-10 (dC 151.3) (Fig. 2). The
H-5 was -oriented, as this compound was also derived from L-
tryptophan. The H-15 was b-oriented in the rearranged skeleton
according to the biogenetic pathway (Fig. 5), in 3 , 5 -tetrahydro-
thereby giving a quaternary Schiff base. The Schiff base can then
potentially be reduced to compound 1 in the presence of NADPH.
Allylic isomerization, moving the vinyl double bond into conjuga-
tion with the iminium, and attack of the oxygen nucleophile on
a
a
a
deoxycordifoline lactam. Combined with the ROESY correlations of
H-3/H-5 and H-15/H-20 (Fig. 3), the relative configuration was
determined.
Mappiodoside G (10), a yellow amorphous powder, was deter-
mined to have a molecular formula of C34H44N2O17 by HRESIMS.
Its UV and IR spectroscopic data were similar to those of
5-carboxystrictosidine. By comparison of the 1H and 13C NMR
spectroscopic data, it differed from 5-carboxystrictosidine through
a, b-unsaturated iminium ion is then hypothesized to generate 3.
Compound 2 could be produced from 3 after decarboxylation and
dehydrogenation. Attack of the C-7 nucleophile on the iminium
intermediate could form the spiro system and eventually yield
compounds 7 and 8. Also, compound 9 could be biosynthesized
by a series of reactions from 5-carboxystrictosidine.
The stereochemistry at C-15 is invariably the same as that of
secologanin, as no reaction has happened at C-15. Therefore, H-
one additional sugar unit. The sugar was determined as
D-glucose
15 is a-oriented in the skeleton of compounds 1–6 and b-oriented
by hydrolysis of 10. The -glucose unit was located at C-10 as
D
in skeleton of compounds 7–9 after rearrangement.
deduced from the HMBC correlation between the proton at dH
4.91 and C-10 at dC 153.2. The methoxyl group was concluded to
be bound to C-22 as reasoned from the HMBC correlation between
OMe (dH 3.81) and C-22 (dC 171.9). The ROESY correlation of
H-3/H-5 indicated that H-3 and H-5 were a-oriented. The proton
coupling constant (J20, 21 = 9.1) and the presence of the ROESY cor-
Table 4
Growth inhibition% @ 100
l
M for four cell lines.
BEL-7402
Compound
HT29
MDA-MB-231
K562
4.5 1.9
1
2
3
4
5
6
7
8
9
10
5.8 0.5
1.5 2.5
2.5 2.9
ꢀ1.5 5.1
7.8 4.8
6.2 3.4
5.7 8.6
6.9 2.9
11.6 4.3
1.3 3.1
3.3 0.2
5.1 4.6
4.6 1.2
ꢀ1.6 3.5
2.1 0.5
11.1 5.3
5.7 5.5
13.1 0.2
15.8 3.2
2.8 5.0
5.7 0.2
0.6 1.2
1.5 1.4
ꢀ3.3 2.6
6.1 2.4
5.0 1.7
2.7 4.3
5.9 1.5
10.1 2.1
ꢀ0.5 0.6
4.9 4.8
3.1 0.9
ꢀ0.4 1.7
4.8 4.3
6.8 0.8
3.8 2.8
9.9 4.2
14.9 4.6
ꢀ0.4 0.5
relation H-15/H-20 suggested that H-15 and H-20 were b-oriented,
and H-21 was
a-oriented. Thus, the relative configuration of 10
was determined.
A biogenetic pathway of the compounds is postulated in Fig. 5.
L-tryptohan combines with secologanin giving a Schiff base. Attack
of the indole C-2 nucleophile on the iminium carbon could then
yield 5-carboxystrictosidine. Hydrolysis of the glycoside function
allows opening of the hemiacetal, and following exposure of the
aldehydic moiety, it can react with the secondary amine function
Vinorelbin was used as positive control with IC50 of 2.6 nM for HT29, 1.2 nM for
BEL-7402, 2.0 nM for MDA-MB-231and 3.4 nM for K562.

H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
83
Compounds 1–10 were evaluated for cytotoxicity against four
rahydro-b-carboline-3-carboxylic acid (20 mg). Fraction I was sub-
human cancer cell lines. However, these compounds did not exhi-
jected to LH-20 CC (MeOH) to give fractions (I1 and I2). Fraction I2
bit significant cytotoxicity (IC50 > 10
(IC50 < 10 nM, Table 4).
l
M), compared to vinorelbin
was separated by RP-HPLC (YMC 5
l
m, 250 ꢁ 10 mm, H2O–CH3CN,
87:13, v/v, 3.0 mL/min, eluting at 10–12 min, UV 254 nm) to yield
compound 3 (60 mg). Fraction J was subjected to C18 CC eluted with
H2O–MeOH (80:20 to 60:40, v/v) to give compound 5-carboxy-
strictosidine (500 mg) and desoxycordifoline (9 mg). Fraction K
was applied to a C18 column eluted with H2O–MeOH (80:20 to
50:50, v/v) to give fractions (K1, K2 and K3). Fraction K1 was sepa-
Conclusions
Ten terpenoid indole alkaloids, mappiodines A-C (1–3) and
mappiodosides A-G (4–10), together with eight known com-
pounds, were isolated from stems of M. iodoides. Their structures
were elucidated by intensive spectroscopic analyses. In previous
phytochemical investigations, five monoterpenoid indole alkaloids
were isolated from M. iodoides stems (Xiao et al., 2011). The find-
ings herein thus complement previous reports of the occurrence
of terpenoid indole alkaloids in the Mappianthus genus. It is
concluded that the rich source of terpenoid indole alkaloids in M.
iodoides might be a useful chemotaxonomic marker of the Map-
pianthus genus.
rated by RP-HPLC (YMC 5
v/v, 3.0 mL/min, eluting at 14–34 min, UV 254 nm) to yield com-
l
m, 250 ꢁ 10 mm, H2O–CH3CN, 85:15,
pound 8 (40 mg) and 9 (25 mg). Fraction K2 was separated by RP-
HPLC (YMC 5
l
m, 250 ꢁ 10 mm, H2O–MeOH, 55:45, v/v, 3.0 mL/
min, eluting at 6.5–12.5 min, UV 254 nm) to yield compound 7
(50 mg) and strictosidinic acid (35 mg). Fraction K3 was separated
by RP-HPLC (YMC 5
3.0 mL/min, eluting at 8–17 min, UV 254 nm) to yield compound
5 (60 mg) and 3 , 5 -tetrahydrodeoxycordifolic acid (20 mg). Frac-
tion L was subjected to a C18 CC eluted with H2O–MeOH (80:20 to
45:55, v/v) to give compound 2 (71 mg) and 3 , 5 -tetrahydrode-
l
m, 250 ꢁ 10 mm, H2O–CH3CN, 84:16, v/v,
a
a
a
a
Experimental
oxycordifoline (55 mg). Fraction M was applied to a C18 CC eluted
with H2O–MeOH (80:20 to 40:60, v/v) to give lyaloside (45 mg).
General
Mappiodine A (1)
Yellow amorphous powder, ½a D23
ꢀ4.0 (c 0.15, MeOH), UV
ꢂ
Optical rotations were measured on a Perkin-Elmer 341 polar-
imeter, whereas UV and IR spectra were recorded on a Shimadzu
UV-2450 and a Perkin-Elmer 577 spectrophotometer, respectively.
NMR spectra were acquired on a Varian Mercury NMR spectrome-
ter operating at 500 MHz for 1H and 125 MHz for 13C. HRESIMS was
measured using an Agilent G6224A TOF spectrometer. Thin-layer
chromatography (TLC) used precoated silicagel GF254 plates (Yan-
tai, People’s Republic of China). Column chromatography (CC) used
(MeOH) (loge) kmax 206 (3.96), 274 (3.58), 311 (3.42); IR (KBr) mmax
3407, 2924, 1724, 1628, 1460, 1383, 1201, 1073, 1041 cmꢀ1; for
13C and 1H NMR spectroscopic data, see Tables 1 and 2. HRESIMS:
m/z 417.2016 [M+H]+ (calcd for C22H29N2O6 +, 417.2020).
Mappiodine B (2)
Yellow amorphous powder, ½a D24
ꢂ
+49.0 (c 0.13, MeOH), UV
Sephadex LH-20 (20–80
Chromatorex C18-OPN (20–45
MCI gel CHP20P (75–150 m, Mitsubishi Chemical Industries Co.,
lm; Amersham Pharmacia Biotech AB),
(MeOH) (loge) kmax 210 (4.06), 233 (4.07), 273 (3.92), 314 (3.94);
lm; Fuji Silysia Chemical Ltd.) and
IR (KBr) mmax 3399, 3089, 1675, 1637, 1577, 1506, 1454, 1328,
1200, 1128, 821, 719 cmꢀ1; for 13C and 1H NMR spectroscopic data,
see Tables 1 and 2. HRESIMS: m/z 351.1340 [M+H]+ (calcd for
l
Ltd.), respectively. b-Cellulase was manufactured by Sinopharm
Chemical Reagent Co., Ltd., Shanghai, People’s Republic of China.
C
20H19N2O4+, 351.1339).
Plant material
Mappiodine C (3)
Yellow amorphous powder, ½a D24
ꢂ
-68.1 (c 0.3, MeOH), UV
Stems of Mappianthus iodoides were collected from Nanning, in
Guangxi Province, PR China, in September 2011, and authenticated
by Prof. Heming Yang. A voucher specimen (No. SIMMMI78) is
deposited at the Herbarium of Shanghai Institute of Materia
Medica, Chinese Academy of Sciences, PR China.
(MeOH) (loge) kmax 224 (4.59), 275 (4.09); IR (KBr) mmax 3420,
2922, 2872, 1630, 1460, 1392, 1209, 1075, 1039 cmꢀ1; for 13C
and 1H NMR spectroscopic data, see Tables 1 and 2. HRESIMS: m/
z 399.1559 [M+H]+ (calcd for C21H23N2O6+, 399.1551).
Mappiodoside A (4)
Extraction and isolation
Yellow amorphous powder, ½a D23
ꢂ
-12.2 (c 0.3, MeOH), UV
(MeOH) (loge) kmax 209 (3.84), 270 (3.48), 311 (3.29); IR (KBr) mmax
Air-dried, powdered stems (5.0 kg) of M. iodoides were extracted
with acetone-H2O (3 ꢁ 20 L, 7:3, v/v, 3 times) at room temperature
for 48 h, respectively. The combined extracts were concentrated to
give a crude extract (420 g), which was partitioned between CHCl3
and H2O to obtain a water-soluble fraction (300 g). The latter was
applied to a MCI gel CHP20P column eluted with H2O–MeOH
(100:0; 80:20; 60:40; 40:60; 0:100, v/v). Fourteen major fractions
(A–N) were obtained. Fraction F was applied to C18 CC, eluted with
H2O–MeOH (90:10 to 80:20, v/v) to give fractions (F1, F2 and F3).
Fraction F1 was further subjected to MCI gel CHP20P CC with
H2O-MeOH (90:10 to 70:30, v/v) to afford 6 (30 mg). Fraction F2
3408, 2923, 1724, 1627, 1459, 1382, 1201, 1074, 1041 cmꢀ1; for
13C and 1H NMR spectroscopic data, see Tables 1 and 2. HRESIMS:
m/z 579.2542 [M+H]+ (calcd for C28H39N2O11+, 579.2548).
Mappiodoside B (5)
Yellow amorphous powder, ½a D24
ꢂ
+11.7 (c 0.1, MeOH), UV
(MeOH) (loge) kmax 210 (3.70), 234 (3.65), 262 (3.55), 312 (3.52);
IR (KBr) mmax 3400, 3089, 1676, 1637, 1577, 1506, 1454, 1329,
1199, 1128 cmꢀ1; for 13C and 1H NMR spectroscopic data, see Ta-
bles
1
and 2. HRESIMS: m/z 513.1875 [M+H]+ (calcd for
C
26H29N2O9+, 513.1868).
was further separated by RP-HPLC (YMC 5
l
m, 250 ꢁ 10 mm,
H2O–MeOH, 75:25, v/v, 3.0 mL/min, eluting at 8.0–15.0 min, UV
254 nm) to yield compound 1 (52 mg) and 4 (40 mg). Fraction F3
was further subjected to MCI gel CHP20P CC with H2O–MeOH
(90:10 to 70:30, v/v) to afford tryptophan (60 mg) and 10
(28 mg). Fraction H was subjected to a C18 CC eluted with H2O-
MeOH (80:20 to 60:40, v/v) to give compound 1-methyl-1,2,3,4-tet-
Mappiodoside C (6)
Yellow amorphous powder, ½a D23
ꢀ18.7 (c 0.2, MeOH), UV
ꢂ
(MeOH) (loge) kmax 225 (4.37), 272 (3.81); IR (KBr) mmax 3419,
2921, 2871, 1629, 1460, 1392, 1209, 1076, 1039, 611 cmꢀ1; for
13C and 1H NMR spectroscopic data, see Tables 1 and 3. HRESIMS:
m/z 561.2085 [M+H]+ (calcd for C27H33N2O11+, 561.2079).

84
H.-J. Cong et al. / Phytochemistry 100 (2014) 76–85
Mappiodoside D (7)
solutions of compounds for 72 h. MTT (4 mg/mL) was added to
Colorless amorphous powder, ½a D20
ꢂ
ꢀ119.0 (c 0.3, MeOH); UV
each well and incubated at 37 °C for a further 4 h, DMSO was added
and absorbance was measured at 570 nm on a microplate spectro-
photometer (Molecular Devices Spectra Max 340, MWG-Biothech,
Inc., Sunnyvale, CA, USA). All tests were performed in triplicate,
(MeOH) (loge) kmax 207 (4.37), 244 (4.26); CD (MeOH) kmax nm
(
D
e
) 215 (+22.2), 240 (ꢀ26.9), 285 (+2.89); IR (KBr) mmax 3421,
2923, 1714, 1656, 1619, 1594, 1471, 1338, 1214, 1174,
1068 cmꢀ1; for 13C and 1H NMR spectroscopic data, see Tables 1
and results are expressed as inhibition% @ 100 lM values.
and 3. HRESIMS: m/z 559.1929 [M+H]+ (calcd for C27H31N2O11
,
+
559.1922).
Acknowledgement
Mappiodoside E (8)
The authors gratefully acknowledge grants from the National
Science & Technology Major Project ‘‘Key New Drug Creation and
Manufacturing Program’’, China (Number: 2009ZX09301-001),
the National Natural Sciences Foundation of China (No. 30901851).
Colorless amorphous powder, ½a D23
ꢀ97.5 (c 0.14, MeOH), UV
ꢂ
(MeOH) (loge) kmax 208 (4.42), 244 (4.21); CD (MeOH) kmax nm
(
D
e
) 207 (ꢀ12.51), 225 (+6.25), 251 (ꢀ5.70), 273 (ꢀ1.95), 287
(ꢀ2.84); IR (KBr) mmax 3420, 2924, 1714, 1657, 1620, 1594, 1471,
1068 cmꢀ1; for 13C and 1H NMR spectroscopic data, see Tables 1
Appendix A. Supplementary data
and 3. HRESIMS: m/z 559.1928 [M+H]+ (calcd for C27H31N2O11
,
+
559.1922).
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.phytochem.2014.
01.004.
Mappiodoside F (9)
Yellow amorphous powder, ½a D24
ꢂ
+70.0 (c 0.1, MeOH), UV
(MeOH) (loge) kmax 224 (4.27), 299 (4.10); IR (KBr) mmax 3383,
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