Schefflerins A - G, new triterpene glucosides from the leaves of Schefflera arboricola

Article abstract of DOI:10.1248/cpb.58.1343

From the 1-BuOH-soluble fraction of a MeOH extract of leaves of Schefflera arboricola, collected in Okinawa, six new lupane glucosides, named schefflerins A - F (1 - 6) and one new dammarane glucoside, named schefflerin G (7), were isolated together with three known compounds, citroside A (8), and oleanane saponins, oleanolic acid (9) and echinocystic acid (10) 3-O-α-L- rhamnopyranosyl(1→4′)-O-β-D-glucuronopynosides. Their structures were elucidated through a combination of spectroscopic analyses and the structure of schefflerin F (6) was determined by X-ray crystallographic method using SPring-8 synchrotron radiation.

Full text of DOI:10.1248/cpb.58.1343

October 2010
Regular Article
Chem. Pharm. Bull. 58(10) 1343—1348 (2010)
1343
Schefflerins A—G, New Triterpene Glucosides from the Leaves of
Schefflera arboricola
a
a
,a
b
c
Zhimin ZHAO, Katsuyoshi MATSUNAMI, Hideaki OTSUKA,* Takakazu SHINZATO, Yoshio TAKEDA,
d
d
Masatoshi KAWAHATA, and Kentaro YAMAGUCHI
a
Department of Pharmacognosy, Graduate School of Biomedical Sciences, Hiroshima University; 1–2–3 Kasumi, Minami-
b
ku, Hiroshima 734–8553, Japan: Subtropical Field Science Center, Faculty of Agriculture, University of the Ryukyus; 1
Sembaru, Nishihara-cho, Nakagami-gun, Okinawa 903–0213, Japan: Faculty of Pharmacy, Yasuda Women’s University;
6
c
d
–13–1 Yasuhigashi, Asaminami-ku, Hiroshima 731–0153, Japan: and Faculty of Pharmaceutical Sciences, Tokushima
Bunri University, Kagawa Campus; 1314–1 Shido, Sanuki, Kagawa 769–2193, Japan.
Received May 17, 2010; accepted July 8, 2010; published online July 9, 2010
From the 1-BuOH-soluble fraction of a MeOH extract of leaves of Schefflera arboricola, collected in Oki-
nawa, six new lupane glucosides, named schefflerins A—F (1—6) and one new dammarane glucoside, named
schefflerin G (7), were isolated together with three known compounds, citroside A (8), and oleanane saponins,
oleanolic acid (9) and echinocystic acid (10) 3-O-a-L-rhamnopyranosyl(1→4؅)-O-b-D-glucuronopynosides. Their
structures were elucidated through a combination of spectroscopic analyses and the structure of schefflerin F (6)
was determined by X-ray crystallographic method using SPring-8 synchrotron radiation.
Key words Schefflera arboricola; Araliaceae; triterpene; lupane glucoside; dammarane glucoside
Schefflera arboricola, native to Taiwan and Hainan, is an
evergreen shrub growing to 3—10 m in height and called as
geraniumleaf aralia or dwarf umbrella tree in English. The
leaves are palmately compound, with 7—9 leaflets in 10—
20 cm length and 4—6 cm width. In Japan, S. arboricola is
sometimes sold at flower shops for an ornamental shrub erro-
neously named as “Kapok.” Kapok (Ceiba pentandra, Mal-
vaceae) is a different tropical tree which produces fiber and
used as an alternative to down. Some oleanane and lupane
1
—3)
triterpene saponins have been isolated from S. arboricola,
4)
5)
6)
7)
S. fagueti, S. rotondifolia, S. divaricata and S. impressa.
Sedative, hypnotic, analgenic, anticonvulsant and smooth
muscle relaxant effects were reported for ethanolic leaf ex-
8)
tract of Schefflera spp.
From a 1-BuOH-soluble fraction of the MeOH extract of
S. arboricola leaves, seven new triterpene saponins, named
schefflerins A—G (1—7) were isolated, together with three
9)
known compounds, citroside A (8), and oleanane saponins,
oleanolic acid (9) and echinocystic acid (10) 3-O-a-L-
1)
rhamnopyranosyl(1→4)-O-b-D-glucuronopynosides. Of the
seven new saponins, schefflerins A—F were found to be lu-
pane (1—5) and nor-lupane (6) triterpene glucosides, and
schefflerin G (7) a dammarane triterpene glucoside. This
paper deals with structure elucidation of them.
Results and Discussion
Air-dried leaves of Schefflera aiboricola were extracted
with MeOH three times and the concentrated MeOH extract
was partitioned with solvents of increasing polarity. The 1-
BuOH-soluble fraction was separated by means of various
chromatographic procedures including column chromatogra-
phy (CC) on a highly porous synthetic resin (Diaion HP-20),
then normal silica gel and reversed-phase octadecyl silica gel
Fig. 1. Compounds Isolated from Schefflera arboricola
(ODS) CC, droplet counter-current chromatography (DCCC), on the basis of spectroscopic evidence and the structure of
and high-performance liquid chromatography (HPLC) to af- schefflerin F (6) was confirmed by X-ray crystallographic
ford 10 compounds (1—10). The details and yields are given analysis. The structures of known compounds were identified
under Experimental. The structures of the new triterpene glu- by comparison of spectroscopic data with those reported in
cosides, schefflerins A—G (1—7) (Fig. 1) were elucidated the literature.
∗
To whom correspondence should be addressed. e-mail: hotsuka@hiroshima-u.ac.jp
© 2010 Pharmaceutical Society of Japan

1
344
Vol. 58, No. 10
2
0
Schefflerin A (1), [a] ϩ23.0, was isolated as an amor- tiple bond correlation (HMBC) spectrum. Thus, the presence
D
phous powder and its elemental composition was determined of dimethyl crabinol moiety was demonstrated and the agly-
to be C H O by high-resolution (HR)-electrospray ioniza- cone was made up with four six-membered and one five-
3
6
62
9
1
1
tion (ESI) MS. Strong absorption bands at 3394 and membered rings. Detailed analyses of H– H correlation
Ϫ1
1
079 cm in the IR spectrum were characteristic founds in spectroscopy, heteronuclear single quantum correlation and
Ϫ1
1
13
glycosidic compounds and an absorption at 2929 cm indi- HMBC spectra allowed the assignment of all the H and
C
cated that schefflerin A (1) had a terpenic structure. In the signals and from the above evidence, the structure of schef-
1
H-NMR spectrum, signals for seven singlet methyls, an iso- flerin A (1) was expected to be a lupane-type triterpene with
lated primary alcohol [d 3.67 (1H, d, Jϭ11 Hz) and 4.17 one b-D-glucopyranose unit. In the HMBC spectrum, the cor-
H
(
1H, d, Jϭ11 Hz)] and one anomeric proton [d 4.98 (1H, d, relation cross peaks between the other set of geminal di-
H
13
Jϭ8 Hz)] were observed. The C-NMR spectrum exhibited methyl signals [dH 2.05 (H -23), 1.42 (H -24)] and d 89.6
3
3
C
six signals assignable to b-glucopyranose, which was deter- placed a hydroxyl group at the 3-postion in an equatorial ori-
mined to be in D-series by HPLC analysis of the acid hy- entation from the coupling constants of H-3 (dd, Jϭ12,
1
3
drolyzate of 1 using a chiral detector. The remaining 30 C- 3 Hz). The doublet carbon resonated at d 61.2 was assigned
NMR signals comprised of seven methyls, ten methylenes, to be C-5 from the HMBC correlations from H -23 and H -
C
3
3
seven methines and six quaternary carbons (Table 1). Judg- 24. The third hydroxyl group was placed at C-6 from cou-
ing from the elemental composition, and absence of any dou- pling patterns and constants of H-5 [dH 1.16 (d, Jϭ12 Hz)]
1
3
ble bond and ketone functional signals in the C-NMR spec- and H-6 [d 4.29 (ddd, Jϭ12, 12, 3 Hz)], which also indi-
H
trum, schefflerin A (1) was presumed to be a pentacyclic cated that the hydroxyl group was in an equatorial orienta-
triterpene. Four oxygen atoms were expected to locate on tion. The primary alcohol determined to be at the 17-position
triplet (d 60.0), doublet (d 67.7, 89.6) and singlet (d 72.4) due to the HMBC correlations of the H -28 with C-16 (d
C
C
C
2
C
carbons due to their relatively deshielded chemical shifts. 30.7), C-17 (d 49.9) and C-22 (d 34.3). The dimethyl
C
C
One set [d 1.36 (H -29), 1.45 (H -30)] of geminal methyl carbinol group (C-20, 29, 30) was placed at the 19-position
H
3
3
signals showed correlation cross peaks with the singlet car- from the HMBC correlations of H-19 (dH 2.13) with C-20
bon (d 72.4) with an oxygen atom in the heteronuclear mul- (d 72.4), C-29 (d 25.6) and C-30 (d 32.3), and H-18 (d
C
C
C
C
H
1.83) with C-20. Other HMBC correlations shown in Fig. 2
1
3
were supportive the lupane skeleton for schefflerin A (1). At-
tachment of the sugar unit at the hydroxyl group at the 3-
positon was also informed from the HMBC correlation cross
peak between H-1Ј and C-3. Therefore, the structure of
schefflerin A (1) was elucidated to be lupane-3b,6a,20,28-
tetraol 3-O-b-D-glucopyranoside, as shown in Fig. 1.
Table 1.
C-NMR Data for Schefflerins A—G (1—7) (C D N, 150 MHz)
5
5
C
1
2
3
4
5
6
7
1
39.1 t
26.7 t
89.6 d
40.5 s
61.2 d
67.7 d
47.6 t
42.9 s
50.5 d
39.0 s
21.8 t
29.2 t
36.6 d
43.9 s
28.0 t
30.7 t
49.9 s
49.3 d
50.8 d
72.4 s
28.6 t
34.3 t
31.5 q
17.0 q
17.5 q
17.7 q
15.5 q
60.0 t
25.6 q
32.3 q
39.4 t
27.9 t
78.8 d
40.2 s
60.8 d
80.4 d
44.9 t
42.9 s
50.7 d
39.7 s
21.9 t
29.2 t
36.7 d
43.9 s
27.6 t
30.7 t
49.8 s
49.3 d
50.7 d
72.5 s
28.6 t
34.2 t
31.8 q
16.4 q
17.7 q
17.9 q
15.3 q
60.1 t
25.6 q
32.2 q
39.4 t
28.0 t
78.8 d
40.3 s
60.8 d
80.4 d
44.8 t
43.0 s
50.9 d
39.8 s
22.0 t
29.1 t
36.6 d
44.0 s
27.6 t
31.7 t
45.5 s
48.2 d
54.2 d
73.2 s
73.6 d
45.4 t
31.8 q
16.3 q
17.8 q
17.9 q
15.5 q
61.7 t
30.4 q
31.4 q
39.4 t
28.0 t
78.8 d
40.3 s
60.9 d
80.2 d
44.9 t
43.0 s
50.5 d
39.7 s
22.0 t
29.0 t
37.3 d
44.8 s
38.0 t
76.4 d
51.0 s
48.0 d
50.3 d
39.4 t
27.9 t
39.3 t
27.9 t
39.6 t
28.0 t
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
78.8 d 78.6 d 78.7 d
40.3 s 40.3 s 40.4 s
60.9 d 61.0 d 61.5 d
80.4 d 80.3 d 80.1 d
44.7 t
42.4 s
2
0
Schefflerin B (2), [a] ϩ14.2, was isolated as colorless
D
needles and its elemental composition was the same as that
of 1. Other physical properties were similar to those of 1 and
44.8 t
41.9 s
45.7 t
41.8 s
13
C-NMR chemical shift of the 3-positon obviously shifted
up (d 78.8) and that of the 6-position shifted down (d
50.6 d 51.0 d 50.9 d
C
C
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
39.8 s
21.3 t
27.4 t
39.9 s
21.2 t
27.6 t
39.9 s
22.0 t
28.1 t
80.4). Since, in the HMBC spectrum, the anomeric proton
(d 4.93) showed a cross peak with C-6, the structure of
H
schefflerin B (2) was concluded to be an isomer of 1 as to the
position of b-D-glucopyranose unit, as shown in Fig. 1.
37.3 d 32.1 d 42.2 d
43.2 s
27.2 t
30.2 t
48.6 s
42.1 s
27.2 t
23.9 t
44.1 s
50.7 d
31.5 t
25.4 t
50.5 d
2
0
Schefflerin C (3), [a] ϩ16, was isolated as an amor-
D
phous powder and its elemental composition was determined
to be C H O , which was one more oxygen atom com-
3
6
62 10
49.6 d 48.1 d 17.7 q
44.2 d 82.0 d 17.3 q
72.4 s 156.5 s
74.1 s
29.0 t
39.0 t
31.8 q
16.4 q
18.0 q
17.7 q
16.7 q
14.6 q
32.4 t
34.7 t
73.2 d 26.1 q
48.0 t
41.6 t
31.8 q 31.7 q 22.9 t
16.4 q 16.4 q 126.5 d
17.6 q 17.8 q 136.1 s
17.8 q 17.5 q 68.2 t
14.8 q 13.2 q 14.0 q
59.3 t
71.6 t
25.6 q
32.2 q
16.6 q
26.1 q 106.2 t
32.1 q 64.3 t
1
2
3
4
5
6
Ј
Ј
Ј
Ј
Ј
Ј
107.2 d 105.8 d 105.8 d 105.7 d 105.8 d 106.1 d 105.9 d
75.9 d
78.8 d
72.0 d
78.0 d
63.2 t
75.4 d
79.6 d
71.7 d
77.9 d
63.0 t
75.4 d
79.7 d
71.8 d
78.0 d
63.0 t
75.5 d
79.6 d
71.8 d
78.0 d
63.0 t
75.4 d 75.5 d 75.5 d
79.6 d 79.6 d 79.6 d
71.8 d 71.9 d 71.9 d
78.0 d 78.1 d 78.0 d
63.0 t
63.1 t
63.2 t
Fig. 2. HMBC Correlations for Schefflerin A (1)
s: C; d: CH; t: CH ; q: CH .
Dual arrowhead curves denote HMBC correlations were observed in both ways.
2
3

October 2010
1345
pared to those of schefflerins A (1) and B (2). Physical data group at the 16-position was concluded to be in the equato-
indicated that schfflerin C (3) was analogous compound to rial orientation. Therefore, the structure of schefflerin D (4)
1
3
schefflerins A and B and C-NMR data for A, B, C and D was elucidated to be lupane-3b,6a,16b,20-tetraol 6-O-b-D-
rings showed strong similarity to those of schefflerin B (2) glucopyranoside, as shown in Fig. 1.
2
0
(
Table 1). NMR signals for the fifth hydroxyl group was ob-
Schefflerin E (5), [a] ϩ7.9, was isolated as an amor-
D
served at d 73.6 (d) with d 4.97 and thus it must be placed phous powder and the elemental composition was C H O .
C
H
36 60
9
at the 21 or 22-position. In the HMBC spectrum, significant Physical data for schefflerin E (5) were also similar to those
1
3
correlation cross peaks between protons (dH 3.67, 4.19) of of preceding compound. C-NMR data for schefflerin E (5)
the primary alcohol and methylene carbon (d 45.4), and were essentially the same as those of schfflerin B (2), except
C
those between the C-22 methylene protons (d 1.60, 3.03) for the presence of an disubstituted double bond [d 156.5
H
C
and C-28 (d 61.7) forced to place the hydroxyl group at the (s) d d 106.2 (t) with d 5.11, 5.48] and a further primary
C
C
H
2
1-position (Fig. 3a). The nuclear Overhauser enhacement alcohol [d 59.3 (t) with d 4.46, 4.50], instead of the disap-
C
H
correlations, observed between H-21 (d 4.97) and H -28 pearance of hydroxyisopropyl group. Only the possible posi-
H
2
(
d 3.67, 4.19), and those between H-19 (d 2.38) and H-21 tion to place the disubstituted double bond was between C-20
H
H
together with H-13 (d 1.97) in the phase-sensitive (PS) rota- and 29, and HMBC correlation of d 5.11 on d 106.2 with
H
H
C
tional Overhauser effect spectroscopy (ROESY) spectrum d 64.3 confirmed the position of the new primary alcohol to
C
were in good accordance to place the hydroxyl group at be at C-30. Therefore, the structure of schefflerin E (5) was
the 21-position in an a-side. (Fig. 3b). Therefore, the stru- elucidated to be lupan-20(29)-ene-3b,6a,28,30-tetraol 6-O-
cture of schefflerin C (3) was elucidated to be lupane- b-D-glucopyranoside, as shown in Fig. 1.
2
0
3
b,6a,20,21a,28-pentaol 6-O-b-D-glucopyranoside, as shown
Schefflerin F (6), [a] ϩ45.3, was isolated as colorless
D
in Fig. 1.
needles and its elemental composition was determined to be
Schefflerin D (4), [a] ϩ12.9, was isolated as an amor- C H O . C-NMR chemical shifts for rings A—C were es-
phous powder and the elemental composition was deter- sentially the same as those of schefflerin B (2). The aglycone
2
0
13
D
33 54
9
mined to be C H O . The results of NMR experiment indi- moiety comprised of only 27 carbons and judging from the
3
6
62
9
cated that the primary alcohol found in aforementioned elemental composition, it must have a hexacyclic structure.
schefflerins disappeared, instead of that, an extra signal for a In the HMBC spectrum, since methylene protons on C-28
1
3
singlet methyl being observed. C-NMR data of the rings A, showed correlation peaks with C-19 (d 82.0), the sixth ring
C
B and C showed good similarity to those of shefflerins B (2) was assumed to form between these carbons through an ether
and C (3), and those of the ring D also resembled those of linkage (Fig. 4). Other HMBC correlations around D, E and
schefflerins A (1) and B (2). The fourth hydroxyl group was F rings also supported this assumption and allowed to place a
placed on either methylene groups in the ring D. The hy- hydroxyl group at the 21-position. Judging from the PS-
droxyl group in question was placed from the correlation ROESY correlations, one (d 3.88) of the methylene protons
H
cross peak between H -28 (d 1.22) and C-16 (d 76.4) in with the b-axial angular proton H-13 (d 1.78) and the other
3
H
C
H
the HMBC spectrum. Based on the triangular PS-ROESY methylene proton (d 3.13) with H-21 proton (d 4.36),
H
H
correlations between a-axial methyl H -27 (d 1.09), a-axial 19,28-epoxy ring was expected in a b-face and the hydroxyl
3
H
proton H-18 (d 1.72) and H-16 (dH 3.95), the hydroxyl group at the 21-positon in an a-face like schefflerin C (3). To
H
confirm the trinor epoxy structure of schefflerin F (6), X-ray
crystallographic experiment was attempted. A crystal was
too small to solve the structure with reliable resolution with a
conventional diffractometer with MoKa radiation. Finally,
X-ray structure was obtained using synchrotron radiation of
Fig. 3. HMBC Correlations (a) and PS-ROESY Correlations (b) of C—E
Rings for Schefflerin C (3)
Fig. 4. Diagnostic HMBC Correlations for Schefflerin F (6)
Dual arrowhead curves in a denote HMBC correlations were observed in both ways.
Dual arrowhead curves denote HMBC correlations were observed in both ways.

1
346
Vol. 58, No. 10
Fig. 6. HMBC Correlations for Schefflerin G (7)
Fig. 5. ORTEP Drawing of Crystallographic Structure of Schefflerin F (6)
Dual arrowhead curves denote HMBC correlations were observed in both ways.
Experimental
the SPring-8 BL38B1 facility. Figure 5 shows an ORTEP
drawing of the crystal structure of schefflerin F (6) and
the structure assumed by spectroscopic data was proved to
be correct. Thus, the structure of schefflerin F (6) was de-
termined to be (19R)-lupan-19,28-epoxy-20,29,30-trinor-
General Experimental Procedure Melting points were measured with
a Yanagimoto micro melting point apparatus and are uncorrected. IR spectra
were obtained on a Horiba Fourier transform infrared spectrophotometer FT-
7
10. Optical rotation data were collected on a JASCO P-1030 polarimeter.
1
13
H- and C-NMR spectra were recorded on a JEOL JNM a-400 spectrome-
ter at 400 and 100 MHz, and a JEOL JNM ECA-600 spectrometer at 600
3
1
b,6a,21a-triol 6-O-b-D-glucopyranoside, as shown in Fig. and 150 MHz, respectively, with tetramethylsilane as an internal standard.
HR-ESI-time-of-flight (TOF) mass spectra (positive-ion mode) were taken
on an Applied Biosystem QSTAR XL System ESI (Nano Spray)-TOF-MS,
respectively.
.
2
0
Schefflerin G (7), [a] ϩ67.5, was isolated as an amor-
D
phous powder and its elemental composition was determined
Highly-porous synthetic resin Diaion HP-20 (Fϭ60 mm, Lϭ65 cm) was
to be C H O by HR-ESI-MS. Physical data also indicated purchased from Mitsubishi Chemical Co., Ltd. (Tokyo, Japan). Silica gel
3
6
62
9
that schefflerin G (7) was a terpenic compound with one column chromatography (CC) was performed on silica gel 60 [(E. Merck,
1
3
Darmstadt, Germany) 70—230 mesh]. Reversed-phase [octadecyl silica gel
ODS)] open CC (RPCC) was performed on Cosmosil 75C -OPN (Nacalai
sugar unit. C-NMR exhibited six signals assignable to b-D-
glucopyranose together with 30 carbon signals, comprised
with seven methyls, ten methylenes, six methines, five qua-
(
1
8
Tesque, Kyoto) [Fϭ50 mm, Lϭ25 cm, linear gradient: MeOH–H O (1 : 9,
2
1.5 l)→(7 : 3, 1.5 l), 10 g fractions being collected]. The droplet counter-cur-
ternary carbons and one trisubstituted double bond. The pres- rent chromatograph (DCCC) (Tokyo Rikakikai, Tokyo, Japan) was equipped
ence of one primary, two secondary and one tertiary alcohols with 500 glass column (Fϭ2 mm, Lϭ40 cm), and the lower and upper layers
were also expected from their chemical shifts. In the H-
NMR spectrum, all methyl signals were appeared as singlets,
one methyl being expected to be on the double bond from its
1
of a solvent mixture of CHCl –MeOH–H O–1-PrOH (9 : 12 : 8 : 2) were used
3 2
as the mobile and stationary phases, respectively. Five gram fractions were
collected and numbered according to their order of elution with the mobile
phase. HPLC was performed on an ODS (Inertsil; GL Science, Tokyo,
chemical shift (d 1.86). Judging from the elemental compo- Japan; Fϭ6 mm, Lϭ25 cm, flow rate: 1.6 ml/min) column.
H
Plant Material Leaves of S. arboricola HAYATA (Araliaceae) were col-
sition, schefflerin G (7) was expected to be a tetracyclic
1
3
lected in Nishihara Town, Nakagami County, Okinawa, Japan, in June 2005,
and a voucher specimen was deposited in the Herbarium of Pharmaceutical
Sciences, Graduate School of Biomedical Sciences, Hiroshima University
05-SA-Okinawa-0629).
Extraction and Isolation Air-dried leaves of S. arboricola (11.0 kg)
were extracted three times with MeOH (45 lϫ3) for one week at room tem-
perature, and then the MeOH extract was concentrated to 6 l in vacuo. The
extract was washed with n-hexane (6 l) and then the methanolic layer was
concentrated to a viscous gum (n-hexane-soluble fraction: 245 g). The
triterpene and C-NMR chemical shifts for A and B rings
were essentially the same as those of schefflerins B—F. From
the HMBC evidence, schefflerin G (7) was deduced to have a
side chain comprised of eight carbon atoms and a tetracyclic
ring system including three six-membered rings and one five-
membered ring (Fig. 6). Therefore, schefflerin G (7) was
considered to be a dammarane triterpene with four hydroxyl
(
groups at C-3, 6, 20, 26. Attachment of the b-glucopyranosyl gummy residue was suspended in H O (6 l) and then extracted with EtOAc
2
moiety was also confirmed to the hydroxyl group at the 6-po- (6 l) to give 245 g of an EtOAc-soluble fraction. The aqueous layer was ex-
tracted with 1-BuOH (6 l) to give 445 g of 1-BuOH-soluble fraction. The re-
maining water-layer was concentrated to furnish 441 g of a water-soluble
fraction. An aliquot of the 1-BuOH-soluble extract (238 g) was applied to
sition. Judging from significant PS-ROESY correlations be-
tween methylene protons (d 4.31) and an olefinic proton
H
(
d 5.83), geometry of the double bond was determined to be
H
Diaion HP-20 CC (Fϭ10.6 cm, Lϭ50 cm), using a stepwise-gradient of
E. Absolute configuration of the 20-position was expected to MeOH–H O [(1 : 4, 12 l), (2 : 3, 12 l), (3 : 2, 12 l) and (4 : 1, 12 l)] and MeOH
2
1
3
be S, by comparison of the C-NMR data for (20R)- (12 l), 1.0 l fractions being collected. The residue eluted with the 40—60%
MeOH (19.1 g in fractions 17—25) obtained on Diaion HP-20 CC was sub-
dammaranediol I (C-17, 21, 22: d 49.9, 24.5, 42.9, respec-
C
jected to silica gel (450 g) CC using CHCl (2 l), CHCl –MeOH [(99 : 1, 2 l),
3
3
tively) and (20S)-dammaranediol II (C-17, 21, 22: d 50.3,
C
(97 : 3, 2 l), (19 : 1, 2 l), (37 : 3, 2 l), (9 : 1, 2 l), (17 : 1, 2 l), (17 : 3, 2 l), (33 : 7,
10)
2
5.3, 41.9, respectively) with those of schefflerin G (7) (C-
2
l), (4 : 1, 2 l), (3 : 1, 2 l) and (7 : 3, 2 l)] , CHCl –MeOH–H O (35 : 15 : 2,
3
2
1
7, 21, 22: d 50.5, 26.1, 41.6, respectively). Accordingly, 4 l), and MeOH (3 l), fractions of 200 ml being collected. The residue (1.23 g
C
in fractions 65—81) of the 12.5% MeOH in CHCl eluate obtained on silica
the structure of schefflerin G (7) was elucidated to be
3
gel CC was subjected to PRCC. The residue (122 mg in fractions 94—113)
was purified by HPLC with 35% MeOH to afford 45.5 mg of 8 from the
peak at 7.5 min.
(
20S,24E)-dammaran-24-ene-3b,6a,20a,26-tetraol 6-O-b-D-
glucopyranoside, as shown in Fig. 1.
The residue (2.78 g in fractions 106—120) of the 30% MeOH in CHCl3

October 2010
1347
eluate obtained on silica gel CC was subjected to PRCC. The residue
ddd, Jϭ13, 4, 4 Hz, H-15a), 2.11 (3H, s, H -23), 1.97 (1H, dd, Jϭ12, 12 Hz,
3
(
1
280 mg in fractions 124—150) was separated by DCCC to give 25.9 mg of H-13), 1.95 (1H, m, H-2a), 1.88 (1H, m, H-2b), 1.82 (1H, m, H-7b), 1.77
0 in fractions 4—5.
(3H, s, H -29), 1.76 (3H, s, H -30), 1.74 (1H, m, H-1a), 1.61 (3H, s, H -24),
3
3
3
The residue eluted with the 60—80% MeOH (21.4 g in fractions 32—37)
1.60 (1H, m, H-22b), 1.59 (1H, m, H-11a), 1.47 (2H, m, H -12), 1.45 (1H,
2
obtained on Diaion HP-20 CC was subjected to silica gel (600 g) CC using
CHCl (3 l), CHCl –MeOH [(99 : 1, 3 l), (97 : 3, 3 l), (19 : 1, 3 l), (37 : 3, 3 l),
br d, Jϭ13 Hz, H-9), 1.41 (1H, d, Jϭ10 Hz, H-5), 1.37 (1H, m, H-16b), 1.24
3
3
(1H, br d, Jϭ13 Hz, H-15b), 1.24 (1H, m, H-11b), 1.20 (3H, s, H -26), 1.05
3
13
(9 : 1, 3 l), (17 : 1, 3 l), (17 : 3, 3 l), (33 : 7, 3 l), (4 : 1, 3 l), (3 : 1, 3 l) and (7 : 3,
(1H, dd, Jϭ13, 13 Hz, H-1b), 1.01 (3H, s, H -25), 0.97 (3H, s, H -27). C-
3
3
3
3
1
l)] , CHCl –MeOH–H O (35 : 15 : 2, 3 l), and MeOH (3 l), fractions of
00 ml being collected. The residue (2.49 g in fractions 68—77) of the 10—
5% MeOH in CHCl3 eluate obtained on silica gel CC was subjected to
NMR (C D N, 150 MHz): Table 1. HR-ESI-MS (positive-ion mode) m/z:
5 5
ϩ
3
2
661.4282 [MϩNa] (Calcd for C H O Na: 661.4286).
36 62 10
2
0
Schefflerin D (4): Amorphous powder, [a] ϩ12.9 (cϭ0.14, MeOH). IR
D
Ϫ1
1
PRCC. The residue (94.2 mg in fractions 124—134) was purified by HPLC
with 50% MeOH to afford 21.7 mg of 6 from the peak at 12 min. The
residue (940 mg in fractions 160—171) afforded 47.0 mg of 2 in a crys-
talline state. The residue (19.8 mg in fractions 206—229) was purified by (1H, m, H-4Ј), 4.28 (1H, dd, Jϭ8, 8 Hz, H-3Ј), 4.15 (1H, dd, Jϭ8, 8 Hz, H-
HPLC with 60% MeOH to afford 6.3 mg of 7 from the peak at 23 min, and
nmax (film) cm : 3412, 2968, 1508, 1086, 1028. H-NMR (C D N,
5 5
600 MHz) d: 5.08 (1H, d, Jϭ8 Hz, H-1Ј), 4.52 (1H, dd, Jϭ12, 3 Hz, H-6Јa),
4.46 (1H, ddd, Jϭ10, 10, 2 Hz, H-6), 4.35 (1H, dd, Jϭ12, 5 Hz, H-6Јb), 4.31
2Ј), 3.99 (1H, m, H-5Ј), 3.95 (1H, m, H-16), 3.61 (1H, dd, Jϭ11, 5 Hz, H-3),
2.72 (1H, dd, Jϭ13, 3 Hz, H-7a), 2.40 (1H, m, H-12a), 2.20 (1H, m, H-19),
2.10 mg of 4 from the peak at 34 min.
The residue (2.35 g in fractions 78—87) of the 15—20% MeOH in CHCl3
2.17 (1H, d, Jϭ13 Hz, H-15a), 2.11 (3H, s, H -23), 2.04 (1H, m, H-22a),
3
eluate obtained on silica gel CC was subjected to PRCC. The residue
81.0 mg in fractions 200—221) was purified by HPLC with 50% MeOH to
afford 39.8 mg of 3 from the peak at 10 min. The residue (122 mg in frac-
tions 229—235) was purified by HPLC with 50% MeOH to afford 41.6 mg H-11a), 1.65 (1H, m, H-12b), 1.58 (1H, m, H-22b), 1.51 (3H, s, H -30), 1.49
of 5 from the peak at 34.4 min. The residue (12.5 mg from the peak at
2.02 (2H, m, H-2a, 21a), 1.95 (1H, m, H-7b), 1.94 (1H, m, H-13), 1.93 (1H,
m, H-2b), 1.84 (1H, dd, Jϭ13, 4 Hz, H-15b), 1.78 (1H, d, Jϭ13 Hz, H-1a),
(
1.72 (1H, m, H-18), 1.70 (1H, m, H-21b), 1.69 (3H, s, H -24), 1.66 (1H, m,
3
3
(1H, m, H-9), 1.47 (1H, d, Jϭ10 Hz, H-5), 1.40 (3H, s, H -29), 1.38 (3H, s,
3
3
2 min) was repeatedly purified by HPLC with 60% MeOH to afford H -26), 1.33 (1H, m, H-11b), 1.22 (3H, s, H -28), 1.11 (3H, s, H -25), 1.09
3
3
3
1
3
9.80 mg of 1 from the peak at 10.5 min.
(3H, s, H -27), 1.08 (1H, m, H-1b). C-NMR (C D N, 150 MHz): Table 1.
3 5 5
ϩ
The residue eluted with the 80—100% MeOH (23.4 g in fractions 49—
3) obtained on Diaion HP-20 CC was subjected to silica gel (550 g) CC
HR-ESI-MS (positive-ion mode) m/z: 661.4287 [MϩNa] (Calcd for
5
C H O Na: 661.4286).
3
6
62
9
2
0
using CHCl3 (2 l), CHCl –MeOH [(99 : 1, 2 l), (97 : 3, 2 l), (19 : 1, 2 l),
Schefflerin E (5): Amorphous powder, [a] ϩ7.9 (cϭ0.59, MeOH). IR
D
Ϫ1 1
3
(37 : 3, 2 l), (9 : 1, 2 l), (17 : 1, 2 l), (17 : 3, 2 l), (33 : 7, 2 l), (4 : 1, 2 l), (3 : 1,
nmax (film) cm : 3395, 2936, 1650, 1457, 1369, 1079. H-NMR (C D N,
5 5
2
l), (7 : 3, 2 l)], CHCl –MeOH–H O (35 : 15 : 2, 2 l) and MeOH (3 l), frac-
600 MHz) d: 5.48 (1H, br d, H-29a), 5.11 (1H, br s, H-29b), 4.94 (1H, d,
Jϭ8 Hz, H-1Ј), 4.50 (1H, d, Jϭ15 Hz, H-30a), 4.46 (1H, d, Jϭ15 Hz, H-
30b), 4.42 (1H, dd, Jϭ12, 3 Hz, H-6Јa), 4.35 (1H, ddd, Jϭ11, 11, 2 Hz, H-
6), 4.30 (1H, dd, Jϭ12, 5 Hz, H-6Јb), 4.25 (1H, dd, Jϭ8, 8 Hz, H-3Ј), 4.22
3
2
tions of 300 ml being collected. The residue (4.00 g in fractions 70—79) af-
forded 21.7 mg of 9 in a crystalline state.
2
0
Schefflerin A (1): Amorphous powder, [a] ϩ23.0 (cϭ0.21, MeOH). IR
D
Ϫ1
1
nmax (film) cm : 3394, 2929, 1457, 1369, 1079, 1035. H-NMR (pyridine- (1H, dd, Jϭ8, 8 Hz, H-4Ј), 4.09 (1H, d, Jϭ11 Hz, H-28a), 4.07 (1H, dd,
d , 400 MHz) d: 4.98 (1H, d, Jϭ8 Hz, H-1Ј), 4.58 (1H, dd, Jϭ11, 2 Hz, H-
Jϭ8, 8 Hz, H-2Ј), 3.91 (1H, ddd, Jϭ8, 5, 3 Hz, H-5Ј), 3.65 (1H, d, Jϭ11 Hz,
H-28b), 3.55 (1H, dd, Jϭ11, 4 Hz, H-3), 2.61 (1H, ddd, Jϭ11, 11, 6 Hz, H-
19), 2.50 (1H, dd, Jϭ11, 2 Hz, H-7a), 2.40 (1H, m, H-16a), 2.39 (1H, m, H-
5
6
4
Јa), 4.39 (1H, dd, Jϭ11, 5 Hz, H-6Јb), 4.29 (1H, ddd, Jϭ12, 12, 3 Hz, H-6),
.25 (1H, m, H-3Ј), 4.22 (1H, m, H-4Ј), 4.17 (1H, d, Jϭ11 Hz, H-28a), 4.08
(1H, dd, Jϭ8, 8 Hz, H-2Ј), 3.99 (1H, ddd, Jϭ8, 5, 2 Hz, H-5Ј), 3.84 (1H, dd, 22a), 2.33 (1H, m, H-21a), 2.03 (3H, s, H -23), 2.02 (1H, m, H-15a), 1.96
3
Jϭ12, 3 Hz, H-3), 3.67 (1H, d, Jϭ11 Hz, H-28b), 2.41 (1H, m, H-16a), 2.40
1H, m, H-22a), 2.38 (1H, m, H-12a), 2.33 (1H, m, H-2a), 2.13 (2H, m, H-
(1H, m, H-2a), 1.90 (2H, m, H-2b, 12a), 1.88 (1H, dd, Jϭ11 Hz, H-18), 1.81
(1H, m, H-7b), 1.78 (1H, m, H-13), 1.69 (1H, br d, Jϭ13 Hz, H-1a), 1.63
(
1
1
1
9, 21a), 2.06 (1H, m, H-15a), 2.05 (3H, s, H -23), 1.95 (1H, dd, Jϭ12,
2 Hz, H-7a), 1.91 (1H, m, H-2b), 1.88 (1H, m, H-7b), 1.84 (1H, m, H-13),
.83 (1H, m, H-18), 1.64 (1H, m, H-21b), 1.60 (1H, m, H-12b), 1.54 (1H, m, (2H, m, H-15b, 16b), 1.22 (1H, m, H-22b), 1.20 (3H, s, H -26), 1.08 (1H, m,
(1H, m, H-21b), 1.62 (1H, m, H-12b), 1.60 (3H, s, H -24), 1.39 (1H, d,
3
3
Jϭ11 Hz, H-5), 1.35 (1H, br d, Jϭ12 Hz, H-9), 1.35 (1H, m, H-11a), 1.26
3
H-1a), 1.53 (1H, m, H-11a), 1.45 (3H, s, H -30), 1.42 (3H, s, H -24), 1.41
H-11b), 1.05 (1H, ddd, Jϭ13, 13, 3 Hz, H-1b), 1.00 (3H, s, H -25), 0.92
3
3
3
1
3
(
1H, m, H-9), 1.36 (4H, m, H-16b, H -29), 1.22 (1H, m, H-11b), 1.18 (3H, s, (3H, s, H -27). C-NMR (C D N, 150 MHz): Table 1. HR-ESI-MS (posi-
3
3 5 5
ϩ
H -27), 1.16 (1H, d, Jϭ12 Hz, H-5), 1.15 (3H, s, H -26), 1.14 (2H, m, H-
1
1
tive-ion mode) m/z: 659.4128 [MϩNa] (Calcd for C H O Na: 659.4129).
36 60 9
3
3
1
3
20
5b, 22b), 0.99 (1H, m, H-1b), 0.91 (3H, s, H -25). C-NMR (pyridine-d5,
Schefflerin F (6): Colorless needles (MeOH), mp 219—221 °C, [a]D
3
Ϫ1
00 MHz): Table 1. HR-ESI-MS (positive-ion mode) m/z: 661.4289
ϩ45.3 (cϭ0.35). IR n
1
(film) cm : 3374, 2933, 1453, 1374, 1077, 1040.
max
H-NMR (C D N, 600 MHz) d: 5.01 (1H, d, Jϭ8 Hz, H-1Ј), 4.51 (1H, dd,
ϩ
[MϩNa] (Calcd for C H O Na: 661.4286).
3
6
62
9
5 5
2
0
Schefflerin B (2): Colorless needles (MeOH), mp 223—226 °C, [a]
Jϭ12, 3 Hz, H-6Јa), 4.36 (1H, dd, Jϭ7, 3 Hz, H-21), 4.33 (1H, m, H-6Јb),
4.31 (1H, m, H-6), 4.29 (1H, br s, H-19), 4.25 (1H, dd, Jϭ8, 8 Hz, H-3Ј),
4.20 (1H, dd, Jϭ8, 8, H-4Ј), 4.09 (1H, dd, Jϭ8, 8 Hz, H-2Ј), 3.96 (1H, ddd,
Jϭ8, 5, 3 Hz, H-5Ј), 3.88 (1H, dd, Jϭ7, 3 Hz, H-28a), 3.51 (1H, dd, Jϭ12,
3 Hz, H-3), 3.13 (1H, br d, Jϭ7 Hz, H-28b), 2.57 (1H, dd, Jϭ12, 3 Hz, H-
D
Ϫ1
ϩ14.2 (cϭ0.62, MeOH). IR n
(film) cm : 3376, 2940, 1460, 1369,
max
1
1
1
4
4
3
157, 1080, 1031. H-NMR (C D N, 400 MHz) d: 4.93 (1H, d, Jϭ8 Hz, H-
5 5
Ј), 4.40 (1H, dd, Jϭ12, 3 Hz, H-6Јa), 4.31 (1H, ddd, Jϭ12, 12, 3 Hz, H-6),
.28 (1H, dd, Jϭ12, 5 Hz, H-6Јb), 4.22 (1H, m, H-3Ј), 4.21 (1H, m, H-4Ј),
.20 (1H, m, H-28a), 4.05 (1H, dd, Jϭ8, 8, Hz, H-2Ј), 3.89 (1H, m, H-5Ј),
7a), 2.05 (3H, s, H -23), 2.04 (1H, m, H-22a), 1.93 (1H, dddd, Jϭ12, 3, 3,
3
.65 (1H, d, Jϭ11 Hz, H-28b), 3.52 (1H, dd, Jϭ11, 4 Hz, H-3), 2.54 (1H, dd, 3 Hz, H-2a), 1.87 (1H, m, H-2b), 1.84 (1H, m, H-18), 1.80 (1H, m, H-7b),
Jϭ12, 3 Hz, H-7a), 2.39 (1H, m, H-22a), 2.38 (1H, m, H-16a), 2.35 (1H, m,
1.78 (1H, m, H-13), 1.66 (1H, m, H-12a), 1.65 (1H, m, H-1a), 1.62 (1H, m,
H-12a), 2.14 (1H, m, H-21a), 2.12 (1H, m, H-19), 2.01 (3H, s, H -23), 1.95
H-15a), 1.59 (3H, s, H -24), 1.54 (1H, m, H-16a), 1.50 (1H, m, H-22b), 1.49
3
3
(2H, m, H-2a, 15a), 1.88 (1H, m, H-2b), 1.85 (1H, m, H-13), 1.82 (1H, m,
(1H, m, H-11a), 1.47 (1H, m, H-16b), 1.40 (1H, dd, Jϭ12, 3 Hz, H-9), 1.38
(1H, d, Jϭ11 Hz, H-5), 1.25 (1H, ddd, Jϭ12, 3, 3 Hz, H-15b), 1.18 (1H, m,
H-12b), 1.16 (1H, m, H-11b), 1.13 (2H, s, H -26), 1.00 (3H, s, H -25), 0.95
H-7b), 1.77 (1H, dd, Jϭ11, 8 Hz, H-18), 1.69 (1H, m, H-1a), 1.63 (1H, m,
H-21b), 1.59 (3H, s, H -24), 1.54 (1H, m, H-11a), 1.44 (3H, m, H -30), 1.40
3
3
3
3
1
3
(1H, m, H-12b), 1.39 (1H, m, H-9), 1.38 (1H, d, Jϭ12 Hz, H-5), 1.32 (3H, s,
(1H, ddd, Jϭ13, 13, 3 Hz, H-1b), 0.81 (3H, s, H -27). C-NMR (C D N,
3
5
5
H -29), 1.28 (2H, m, H-15b, 16b), 1.20 (3H, s, H -26), 1.14 (1H, m, H-11b),
150 MHz): Table 1. HR-ESI-MS (positive-ion mode) m/z: 617.3650
3
3
1
3
ϩ
1
(
[
.10 (1H, m, H-22b), 1.01 (6H, s, H -25, 27), 0.97 (1H, m, H-1b). C-NMR [MϩNa] (Calcd for C H O Na: 617.3660).
3
33 54 9
2
0
C D N, 100 MHz): Table 1. HR-ESI-MS (positive-ion mode) m/z: 661.4282
Schefflerin G (7): Amorphous powder, [a] ϩ67.5 (cϭ0.24, MeOH). IR
D
Ϫ1 1
5
5
ϩ
MϩNa] (Calcd for C H O Na: 661.4286).
Schefflerin C (3): Amorphous powder, [a] ϩ16 (cϭ0.87, MeOH). IR
nmax (film) cm : 3732, 2938, 1509, 1456, 1392, 1033, 670. H-NMR
(C D N, 600 MHz) d: 5.83 (1H, dd, Jϭ7, 7 Hz, H-24), 5.20 (1H, d, Jϭ8 Hz,
36
62
9
2
0
D
5
5
Ϫ1
1
n
6
(film) cm : 3367, 2945, 1650, 1457, 1368, 1080. H-NMR (C D N,
H-1Ј), 4.49 (1H, dd, Jϭ12, 3 Hz, H-6Јa), 4.42 (1H, ddd, Jϭ10, 10, 3 Hz, H-
max
5
5
00 MHz) d: 4.98 (1H, d, Jϭ8 Hz, H-1Ј), 4.97 (1H, m, H-21), 4.40 (1H, dd, 6), 4.34 (1H, dd, Jϭ12, 3 Hz, H-6Јb), 4.31 (2H, s, H -26), 4.24 (1H, m, H-
2
Jϭ11, 3 Hz, H-6Јa), 4.34 (1H, ddd, Jϭ10, 10, 3 Hz, H-6), 4.29 (1H, dd,
Jϭ11, 5 Hz, H-6Јb), 4.19 (1H, d, Jϭ11 Hz, H-28a), 4.25 (1H, m, H-3Ј), 4.23 5, 3 Hz, H-5Ј), 3.54 (1H, br d, Jϭ10 Hz, H-3), 2.54 (1H, m, H-23a), 2.50
1H, m, H-4Ј), 4.07 (1H, dd, Jϭ8, 8 Hz, H-2Ј), 3.95 (1H, ddd, Jϭ8, 5, 3 Hz, (1H, dd, Jϭ12, 3 Hz, H-7a), 2.45 (1H, m, H-23b), 2.13 (1H, m, H-12a), 2.06
3Ј), 4.22 (1H, m, H-4Ј), 4.08 (1H, dd, Jϭ8, 8 Hz, H-2Ј), 3.92 (1H, ddd, Jϭ9,
(
H-5Ј), 3.67 (1H, d, Jϭ11 Hz, H-28b), 3.55 (1H, dd, Jϭ12, 3 Hz, H-3), 3.03
1H, dd, Jϭ12, 7 Hz, H-22a), 2.51 (1H, dd, Jϭ10, 3 Hz, H-7a), 2.38 (1H, m,
H-19), 2.34 (1H, m, H-16a), 2.22 (1H, m, dd, Jϭ12, 12 Hz, H-18), 2.12 (1H,
(3H, s, H -29), 1.96 (1H, m, H-2a), 1.96 (1H, m, H-17), 1.95 (1H, m, H-7b),
3
(
1.94 (1H, m, H-13), 1.89 (1H, m, H-2b), 1.86 (3H, s, H -27), 1.85 (1H, m,
3
H-22a), 1.82 (2H, m, H -16), 1.78 (1H, m, H-22b), 1.69 (1H, m, H-1a), 1.65
2

1
348
Vol. 58, No. 10
(
1H, m, H-15a), 1.60 (3H, s, H -28), 1.54 (1H, m, H-11a), 1.48 (1H, dd,
the Hiroshima University Faculty of Medicine and an Applied Biosystem
QSTAR XL system ESI (Nano Spray)-MS at the Analysis Center of Life
3
Jϭ13, 3 Hz, H-9), 1.45 (1H, d, Jϭ10 Hz, H-5), 1.41 (3H, s, H -21), 1.35
3
(
1
1H, m, H-12b), 1.20 (1H, m, H-15b), 1.19 (1H, m, H-11b), 1.16 (3H, s, H - Science of the Graduate School of Biomedical Sciences, Hiroshima Univer-
9), 1.05 (1H, m, H-1b), 1.03 (3H, s, H -18), 0.88 (3H, s, H -30). C-NMR sity. The authors are also grateful for the use of the NMR instrument (JEOL
3 3
3
1
3
(
C D N, 100 MHz): Table 1. HR-ESI-MS (positive-ion mode) m/z: 661.4291 ECA-600) at the Natural Science Center for Basic Research and Develop-
5 5
ϩ
[
MϩNa] (Calcd for C H O Na: 661.4286).
ment, Hiroshima University. This work was supported in part by Grants-in-
X-Ray Crystallographic Analysis of Schefflerin F (6) A suitable crys- Aid from the Ministry of Education, Culture, Sports, Science and Technol-
tal (0.31 mmϫ0.03 mmϫ0.03 mm) was used for analysis. The data were ogy of Japan, the Japan Society for the Promotion of Science, and the Min-
measured using synchrotron radiation (lϭ0.70000 Å) (SPring-8 BL38B1). istry of Health, Labour and Welfare. Thanks are also due to the Astellas
The structure was solved by a direct method using the program SHELXL-97 Foundation for Research on Medicinal Resources and the Takeda Science
36
62
9
11)
(
Sheldrick, 2008). The refinement and all further calculations were carried
Foundation for the financial support. The synchrotron radiation experiments
out using SHELXL-97 (Sheldrick, 2008). The H atoms were included were performed using the beam line, BL38B1 in the SPring-8 with the ap-
at calculated positions and treated as riding atoms using the SHELXL proval of the Japan Synchrotron Radiation Research Institute (JASRI) (Pro-
11)
default parameters. The non-H atoms were refined anisotropically, using posal No. 2009A1880).
2
weighted full-matrix least-squares on F . Crystal Data: C H O ·2.5H O, Mϭ
3
3
54
9
2
Ϫ1
6
34.76 g mol , triclinic, P , aϭ8.693(5) Å, bϭ12.853(5) Å, cϭ14.781(5) Å,
aϭ100.941(5)°, bϭ91.113(5)°, gϭ103.604(5)°, Vϭ1572.4(12) Å ,
Tϭ293(2) K, Zϭ2, D ϭ1.341 Mg/m . Final goodness-of-fit on F was 1.356
References
1
3
1) Melek F. R., Miyase T., Khalik S. M. A., El-Ginidi M. R., Phytochem-
istry, 63, 401—407 (2003).
3
2
c
and final R indices were R ϭ0.0823 and wR ϭ0.2456 based on IϾ2s(I).
2) Guo F.-J., Chen P., Peng S.-Y., Li Y.-C., Helv. Chim. Acta, 89, 468—
474 (2006).
1
2
Ϫ3
The largest difference of the peak and the hole was 0.003 and Ϫ0.001 eÅ
,
respectively. CCDC deposit contains the supplementary crystallographic
data. These data can be obtained free of charge via http://www.ccdc.
cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.; fax: (ϩ44) 1223
3) Abdel Khalik S. M., Al-Azhar J. Pharm. Sci., 28, 39—47 (2001).
4) Cioffi G., Braca A., Autore G., Morelli I., Pinto A., Venturella F., De
Tommasi N., Planta Med., 69, 750—756 (2003).
5) Braca A., Autore G., De Simone F., Marzocco S., Morelli I., Ven-
turella F., De Tommasi N., Planta Med., 70, 960—966 (2004).
6) De Tommasi N., Pizza C., Bellino A., Venturella P., J. Nat. Prod., 60,
663—668 (1997).
336 033; or e-mail: deposit@ccdc.cam.ac.uk.
Analyses of the Sugar Moiety About 500 mg each of schefflerins A—G
1—7) was hydrolyzed with 1 N HCl (0.1 ml) at 90 °C for 2 h. The reaction
(
mixtures were partitioned with an equal amount of EtOAc (0.1 ml), and the
water layers were analyzed with a chiral detector (JASCO OR-2090plus) on
an amino column [Asahipak NH P-504E, CH CN–H O (4 : 1), 1 ml/min].
7) Scrivastova S. K., J. Nat. Prod., 55, 810—813 (1992).
8) Liao N., “Pharmacological and Applications of Chinese Materia Med-
ica,” Vol. 1, ed. by Chang H. M., But P. P. H., World Scientific Press,
Singapore, 1996, p. 6.
9) Umehara K., Hattori I., Miyase T., Ueno A., Hara S., Kageyama C.,
Chem. Pharm. Bull., 36, 5004—5008 (1988).
2
3
2
All the hydrolyzates gave a peak for D-glucose at the retention time of
.5 min (positive optical rotation sign). The peak was identified by co-chro-
9
matography with authentic D-glucose.
10) Asakawa J., Kasai R., Yamasaki K., Tanaka O., Tetrahedron, 33,
Acknowledgements The authors are grateful for access to the supercon-
1935—1939 (1977).
ducting NMR instrument at the Analytical Center of Molecular Medicine of
11) Sheldrick G. M., Acta Crystallogr., A64, 112—122 (2008).