Schoepfiajasmins A-H: C-glycosyl dihydrochalcones, dihydrochalcone glycoside, C-glucosyl flavanones, flavanone glycoside and flavone glycoside from the branches of schoepfia jasminodora

Article abstract of DOI:10.1248/cpb.c13-00466

From the branches of Schoepfia jasminodora collected in Okinawa, three new dihydrochalcone C-glycosides, one dihydrochalcone di-O-glucopyranoside, two flavanone C-glycosides, one flavanone O-glycoside and one flavone O-glycoside were isolated. Their structures were elucidated by extensive study of one- and twodimensional NMR spectroscopic data.

Full text of DOI:10.1248/cpb.c13-00466

1136
Regular Article
Chem. Pharm. Bull. 61(11) 1136–1142 (2013)
Vol. 61, No. 11
Schoepfiajasmins A–H: C-Glycosyl Dihydrochalcones, Dihydrochalcone
Glycoside, C-Glucosyl Flavanones, Flavanone Glycoside and Flavone
Glycoside from the Branches of Schoepfia jasminodora
Kouki Ukida,a Takashi Doi,a Sachiko Sugimoto,a Katsuyoshi Matsunami,a
,a,b
Hideaki Otsuka,* and Yoshio Takedab
a Graduate School of Biomedical and Health Sciences, Hiroshima University; 1–2–3 Kasumi, Minami-ku, Hiroshima
b
734–8553, Japan: and Faculty of Pharmacy, Yasuda Women’s University; 6–13–1 Yasuhigashi, Asaminami-ku,
Hiroshima 731–0153, Japan.
Received June 12, 2013; accepted August 23, 2013
From the branches of Schoepfia jasminodora collected in Okinawa, three new dihydrochalcone C-glyco-
sides, one dihydrochalcone di-O-glucopyranoside, two flavanone C-glycosides, one flavanone O-glycoside and
one flavone O-glycoside were isolated. Their structures were elucidated by extensive study of one- and two-
dimensional NMR spectroscopic data.
Key words Schoepfia jasminodora;ꢀOlacaceae;ꢀchalcone;ꢀflavanone;ꢀflavone
Schoepfia jasminodora is the only species belonging to the ited absorptions attributable to hydroxy groups (3367cm−1),
Olacaceae growing wild in Japan. Leaves of S. jasminodora, a carbonyl group and aromatic ring(s). The UV absorption
collected in Okinawa, afforded the gallates of isoorientin and bands also supported the presence of aromatic ring(s). The
(2S)-1,2-propanediol glucoside. As expected from the presence 1H-NMRꢀ spectrumꢀ exhibitedꢀ signalsꢀ forꢀ fiveꢀ intricatelyꢀ
of gallate in the molecules, the compounds isolated from the coupled and two ortho-coupled aromatic protons, anomeric
leaves showed strong 1,1-diphenyl-2-picrylhydrazil (DPPH) protons [δH 4.72 (1H, d, J=9.6Hz), 5.18 (1H, d, J=1.0Hz)],
radical-scavenging activity.1) A related Brazilian Olacaceous two methylene protons [δH 2.96 (2H, t, J=7.2Hz), 3.24 (2H,
plant, Ptychopetalum olacoides, is called Muira Puama, and t, J=7.2Hz)] coupled to each other and a highly deshielded
used as a tonic and an aphrodisiac. Isolation of clerodane hydroxy proton at δH 13.13. In the 13C-NMRꢀ spectrum,ꢀ fiveꢀ
diterpenoids from P. olacoides and their NGF-potentiating typical signals [δC 109.0 (d), 76.4 (d), 78.9 (s), 73.6 (t), 64.7
activity were reported.2) Nothing was reported until our in- (t)] assigned to those of a terminal apiofuranoside, and 13 sp2
vestigation of the leaves of S. jasminodora, constituents of its carbon and two methtylene signals together with six signals
branches being reported.
for a sugar moiety were observed (Table 1). Of the 13 sp2
From the branches of S. jasminodora, eight new di- signals, one was assigned to a carbonyl functional group from
hydrochalcone,ꢀ flavanoneꢀ andꢀ flavoneꢀ C-glycosides and its highly deshielded chemical shift (δC 203.9), the remaining
O-glycosides,ꢀ namedꢀ schoepfiajasminꢀ A–Hꢀ (1–8), were iso- 12 signals being expected to represent mono- (A ring) and
lated (Fig. 1), along with 14 known compounds, pentyl O- tetrasubstituted (B ring) aromatic rings. In the heteronuclear
β-(2′-O-β-D-glucopyranosyl)-D-glucopyranoside (9),3) benzyl multiple-bond correlation (HMBC) spectrum, one of the
O-β-(6′-O-β-D-apiofuranosyl)-D-glucopyranoside (10),4) zizy- ortho-coupled aromatic protons (δH 7.73) showed a cross peak
beoside (11),5,6) vanilloloside (12),7) β-hydroxypropiovanillone with the carbonyl carbon, and the H2-β protons (δH 2.96) with
3-O-β-D-glucopyranoside (13),8) syringin (14),9) syringare- the carbonyl carbon and aromatic carbon (δC 128.2), as well as
sinol 4′-O-β-D-glucopyranoside (15),10)ꢀ schoepfinsꢀ Bꢀ (16) and H2-α (δH 3.24) with C-1 (δC 141.0) (Fig. 2). Thus, the structure
C
(17),11) 2′,4,4′-trihydroxy-3′-C-glucopyranosyl chalcone of the aglycone moiety was established to have a dihydrochal-
(18),12) pinocembrin 7-O-glucopyranoside (19),13) (2S)-8-C-β- cone skeleton. The heteronuclear single quantum correlation
glucopyranosyl-7-hydroxyflavanoneꢀ (20),1) isovitexin (21),14) spectrum (HSQC) between the anomeric proton (δH 4.72) and
and chrysin 7-O-β-D-glucopyranoside (22).15) The structures of δCꢀ72.0ꢀindicatedꢀthatꢀshoepfijasminꢀAꢀ(1) is a 3′-C-glycoside,
the new compounds were elucidated by detailed examination and the HMBC correlations between the anomeric proton and
of spectroscopic data and those of the known compounds were C-2′, 3′ and 4′ supported this assumption. On acid hydrolysis
identifiedꢀbyꢀcomparisonꢀwithꢀreportedꢀdataꢀinꢀtheꢀliterature.
of 1,ꢀschoepfinꢀBꢀ(16)11) and D-apiose were obtained. The abso-
luteꢀconfigurationꢀofꢀapioseꢀwasꢀdeterminedꢀbyꢀHPLCꢀanalysisꢀ
with a chiral detector and the sugar linkage was determined
Results and Discussion
From the 1-BuOH-soluble fraction of a MeOH extract of to be on the hydroxy group at the C-2″ position from the
branches of S. jasminodora,ꢀ chalconeꢀ andꢀ flavonoidꢀ glyco- HMBC correlation cross peak between the anomeric proton
sides were isolated by various kinds of chromatography. Their (δH 5.18) and C-2″ (δCꢀ74.7).ꢀTheꢀabsoluteꢀconfigurationꢀofꢀtheꢀ
structures were elucidated from physico-chemical evidence.
2-position of D-apiose must be Rꢀ andꢀ judgingꢀ fromꢀ theꢀ smallꢀ
SchoepfiajasminꢀAꢀ(1): [α]D25 −19.7, was isolated as an amor- coupling constant of the anomeric proton (J=1.0Hz), both
phous powder and its elemental composition was determined oxygens at the 1‴- and 2‴-positions took up quasi-axial ori-
to be C26H32O12 by high-resolution (HR)-electrospray ioniza- entations, i.e., β-D-apiofuranoside. Therefore, the structure of
tion (ESI)-mass spectrometry (MS). The IR spectrum exhib- schoepfiajasminꢀAꢀ(1) was elucidated to be as shown in Fig. 1.
SchoepfiajasminꢀBꢀ(2): [α]D25 −21.7, was isolated as an amor-
phous powder and its elemental composition was determined
Theꢀauthorsꢀdeclareꢀnoꢀconflictꢀofꢀinterest.
© 2013 The Pharmaceutical Society of Japan
*ꢀToꢀwhomꢀcorrespondenceꢀshouldꢀbeꢀaddressed.ꢀ e-mail:ꢀhotsuka@hiroshima-u.ac.jp

November 2013
1137
Fig.ꢀ 1.ꢀ StructuresꢀofꢀSchoepfiajasminsꢀA–Hꢀ(1–8)ꢀandꢀSchoepfinꢀBꢀ(16)
were essentially superimposable on those of 1 and 2 (Table
1),ꢀ someꢀ modificationꢀ hadꢀ occurredꢀ inꢀ theꢀ disubstitutedꢀ Aꢀ
ring. The A ring was not symmetrically substituted and thus
the phenolic alcohol functional group was placed on the rare
3-position from the HMBC correlations from H2-β (δH 2.94)
to C-2 (δC 116.3) with δH 6.68 (1H, d, J=2.4Hz) and C-6 (δC
120.7) with δH 6.70 (1H, dd, J=7.9, 2.4Hz) (Fig. 3). Therefore,
theꢀstructureꢀofꢀschoepfiajasminꢀCꢀ(3) was elucidated to be as
shown in Fig. 1.
Schoepfiajasminꢀ Dꢀ (4): [α]D22 −86.0, was isolated as an
amorphous powder and its elemental composition was de-
termined to be C27H34O14 by HR-ESI-MS. The NMR spec-
troscopic data indicated the presence of a monosubstituted
benzene ring (C-1 to C-6) (A ring), which was seen in 1, and
Fig.ꢀ 2.ꢀ HMBCꢀCorrelationsꢀforꢀSchoepfiajasminꢀAꢀ(1)
Arrowheads denote C and arrow tails H.
to be C26H32O13 by HR-ESI-MS. The spectroscopic data were two aromatic protons on the B ring were coupled in a meta
similar to those of 1 and the monosubstituted aromatic ring relationship. Twelve 13C-NMR signals assignable to two sets
must be replaced by a para-subsittuted one with an oxygen of terminal glucopyranosides were also observed (1: δC 99.8,
atom (δC 130.8, 128.7×2, 114.9×2, 155.2). Therefore, the struc- 101.6, 2: δC 73.3, 73.4, 3: δC 77.2, 77.3, 5: δC 76.7, 76.9, and 6:
ture of 2 was determined to be as shown in Fig. 1.
δC 61.1, 61.2). In the acid hydrolyzate of 4, D-glucose was iden-
SchoepfiajasminꢀCꢀ(3): [α]D26 −32.6, was also isolated as an tifiedꢀasꢀaꢀsugarꢀcomponentꢀonꢀHPLCꢀanalysisꢀusingꢀaꢀchiralꢀ
amorphous powder and its elemental composition determined detector. The mode of sugar linkage was determined to be β,
by HR-ESI-MS was the same as that of 2. Spectroscopic judgingꢀ fromꢀ theirꢀ couplingꢀ constantsꢀ ofꢀ anomericꢀ protonsꢀ
dataꢀ indicatedꢀ thatꢀ schoepfiajasminꢀ Cꢀ (3) was an analogous (7.4, 7.7Hz). Since in the HMBC spectrum, both of the meta-
compound to 1 and 2. Since the 13C-NMR data for the sugar coupled aromatic protons [δH 6.17 (1H, d, J=2.0Hz), 6.39 (1H,
moiety, and the B ring region together with two methylenes d, J=2.0Hz)] showed correlation cross peaks with C-1′ (δC

1138
Vol. 61, No. 11
Table 1. 13C-NMRꢀSpectroscopicꢀDataꢀforꢀSchoepfiajasminsꢀA–Dꢀ(1–4) and 2′,4′,6′-Trihydroxychalcone (17)
C
1a)
2a)
3b)
4c)
17d)
1
141.0
128.2
128.2
125.9
128.2
128.2
38.6
130.8
128.7
114.9
155.2
114.9
128.7
38.8
144.0 (142.4)c)
116.3 (113.1)
158.5 (157.4)
114.1 (112.1)
130.5 (129.1)
120.7 (118.9)
40.4 (38.6)
31.7 (30.3)
205.8 (nd)
141.4
128.1
128.2
125.6
128.2
128.1
44.6
141.2
127.7
127.7
125.2
127.7
127.7
44.4
2
3
4
5
6
α
β
C=O
1′
2′
3′
4′
5′
6′
1″
2″
3″
4″
5″
30.2
29.2
29.7
29.6
203.9
112.1
163.6
112.3
163.6
108.2
131.8
72.0
203.9
111.7
163.2
111.9
163.2
107.9
131.4
71.6
203.5
108.2
159.8
95.0
203.3
103.1
163.6
94.1
113.0 (112.0)
165.4 (nd)
114.0 (112.0)
165.4 (nd)
161.5
98.1
164.0
163.6
94.1
110.0 (108.5)
133.3 (131.6)
74.0 (72.0)
76.5 (74.7)
80.9 (79.2)
71.8 (70.8)
80.6 (81.1)
62.8 (61.4)
110.9 (108.9)
78.1 (76.5)
80.6 (78.9)
75.1 (73.6)
66.3 (64.7)
162.7
101.0
73.3
74.7
74.5
79.3
78.9
77.3
70.8
70.4
70.1
81.1
80.7
76.7
6″
61.4
61.1
61.1
1‴
2‴
3‴
4‴
5‴
6‴
109.0
76.4
108.7
76.2
99.8
73.4
78.9
78.6
77.2
73.6
73.2
70.2
64.7
64.4
76.9
61.2
a) Data for DMSO-d6 at 95°C and 150MHz. b) Data for CD3OD at 35°C and 100MHz. c) Data for DMSO-d6 at 95°C and 100MHz. d) Data for (CD3)2CO at 150MHz.16)
nd: not detected.
(3441 cm−1), a ketone functional group (1674cm−1), and an
aromatic ring(s) (1594cm−1), and the UV absorptions were
also consistent with the presence of an aromatic ring(s). The
13C-NMR spectrum exhibited 13 sp2 signals, which comprised
those of one carbonyl carbon and two aromatic rings. One
methylene, one oxygenated methine and six signals assign-
able to a C-glucosyl moiety were also observed (Table 2). In
1
the H-NMR spectrum, two aromatic signals were coupled in
an orthoꢀrelationshipꢀandꢀfiveꢀaromaticꢀsignalsꢀwereꢀexpectedꢀ
be on one aromatic ring (Table 2). One (δH 7.73) of the ortho
coupled aromatic protons showed a correlation cross peak
with the carbonyl carbon (δC 193.5) in the HMBC spectrum,
thus the ortho-coupled aromatic protons were placed at the
H-5 and H-6 positions, and further correlations between H-2
Fig.ꢀ 3.ꢀ HMBCꢀCorrelationsꢀforꢀSchoepfiajasminꢀCꢀ(3)
Arrowheads denote C and arrow tails H.
108.2), the substitution pattern in the B ring was expected to (δH 5.51) and C-2′ (δC 127.3), and H2-3 (δH 2.84, 3.00) and the
be a 2,4,6- or 3,4,5-trihydroxy symmetrical system and the carbonyl carbon and C-1′ (δC 140.6) were observed. A crucial
asymmetry in the B ring was induced by 2,4- or 3,4-di-O-β- HMBCꢀcorrelationꢀfromꢀH-2ꢀtoꢀC-9ꢀestablishedꢀtheꢀflavanoneꢀ
D-glucopyranosylation, respectively. From biosynthetic point skeleton. The position of C-glucosylation was determined to
of view, 2,4,6-substitution was more plausible, and the high be at C-8 from the HMBC correlations from the anomeric
fieldꢀshiftsꢀofꢀtheꢀC-1′, C-3′ and C-5′ signals in the 13C-NMR proton to C-7, C-8 and C-9. Therefore, the C-7 position carried
spectrum supported this fact. The reported spectroscopic data aꢀ hydroxyꢀ groupꢀ judgingꢀ fromꢀ itsꢀ deshieldedꢀ chemicalꢀ shiftꢀ
for its aglycone (17) further supported the substitution patt- (δC 165.4) and the structure was elucidated to be as shown in
tern.16)ꢀ Therefore,ꢀ theꢀ structureꢀ ofꢀ schoepfiajasminꢀ Dꢀ (4) was Fig.ꢀ1.ꢀTheꢀabsoluteꢀconfigurationꢀatꢀtheꢀC-2ꢀpositionꢀwasꢀde-
elucidated to be 2′,4′,6′-trihydroxydihydrochalcone 2′,4′-di-O- termined to be R from the positive and negative Cotton effects
β-D-glucopyranoside, as shown in Fig. 1.
at 301nm and 334nm, respectively, in the circular dichroism
Schoepfiajasminꢀ Eꢀ (5): [α]D26 +45.7, was isolated as an (CD) spectrum.17,18)
amorphous powder and its elemental composition was de-
SchoepfiajasminꢀFꢀ(6): [α]D25 +28.0, was isolated as an amor-
termined to be C21H22O8 by HR-ESI-MS. The IR spectrum phous powder and its elemental composition was determined
exhibited absorption bands attributable to a hydroxy group to be C21H22O9 by HR-ESI-MS. The spectroscopic data indi-

November 2013
1139
1
Table 2. 13C-NMRꢀSpectroscopicꢀDataꢀforꢀSchoepfiajasminsꢀE–Hꢀ(5–8)
methylene protons observed in the H-NMR spectrum were
replacedꢀ byꢀ anꢀ olefinicꢀ protonꢀ atꢀ δH 7.04. Thus, 8 was ex-
pectedꢀtoꢀhaveꢀaꢀflavoneꢀskeletonꢀandꢀitsꢀstructureꢀisꢀasꢀshownꢀ
in Fig. 1.
C
5a)
6b)
7c)
8c)
2
80.8
45.4
80.9
45.2
78.6
42.1
163.7
105.6
182.1
161.1
99.5
3
4
From the branches of S. jasminodora, three relatively rare
dihydrochacone C-glycosides (1–3) and di-O-glucopyranoside
(4)ꢀ wereꢀ isolated.ꢀ Shoepfiajasminꢀ Cꢀ (3) possesses only one
hydroxy functional group at the C-3 position on the benzene
ring. This is a rare substitution pattern and is not frequently
found as a natural product. When 3-hydroxycinnamic acid
was fed to metabolically engineered yeast, the isolation of
3-hydroxydihydrochalcone was reported.19)
193.5
129.5
112.1
165.4
113.5
163.9
115.5
140.6
127.3
129.6
129.4
129.6
127.3
75.9
193.9
129.4
112.0
165.4
113.5
164.1
115.5
131.7
129.0
116.3
158.8
116.3
129.0
75.9
196.7
162.9
96.5
5
6
7
164.9
95.4
163.7
94.9
8
9
162.5
103.3
138.4
126.7
128.5
128.6
128.5
126.7
97.7
157.0
105.4
130.5
126.4
129.1
132.1
129.1
126.4
98.1
10
1′
2′
3′
4′
5′
6′
1″
2″
3″
4″
5″
6‴
1‴
2‴
3‴
4‴
5‴
Experimental
General Experimental Procedures Optical rotations
were measured on a JASCO P-1030 digital polarimeter.
IR and UV spectra were measured on Horiba FT-710 and
JASCO V-520 UV/Vis spectrophotometers, respectively. 1H-
and 13C-NMR spectra were taken on a JEOL JNM α-400
spectrometer at 400MHz and 100MHz, respectively, with
tetramethylsilane as an internal standard. CD spectra were
measured with a JASCO J-720 spectropolarimeter. Positive-
ion HR-ESI-MS was performed with an Applied Biosystems
QSTAR XL NanoSpray™ System.
72.9
72.8
75.7
75.8
80.0
80.0
76.7
76.7
71.8
71.9
69.7
69.8
82.5
85.2
76.9
76.7
62.9
63.0
60.5
60.5
108.7
76.0
108.7
76.0
A highly-porous synthetic resin (Diaion HP-20) was pur-
chased from Mitsubishi Kagaku (Tokyo, Japan). Silica gel CC
was performed on silica gel 60 (E. Merck, Darmstadt, Ger-
many), and ODS open CC on Cosmosil 75C18-OPN (Nacalai
Tesque, Kyoto, Japan) [Φ=45mm, L=25cm; H2O–MeOH
(9:1, 1L)→(1:9, 1L), linear gradient, 10g fractions being
collected]. The DCCC (Tokyo Rikakikai, Tokyo, Japan) was
79.2
79.2
73.9
73.9
64.2
64.1
a) Data for CD3OD at 35°C and 100MHz. b) Data for CD3OD at 35°C and
150MHz. c) Data for DMSO-d6 at 35°C and 150MHz.
catedꢀthatꢀschoepfiajasminꢀFꢀ(6) was a similar compound to 5 equipped with 500 glass columns (Φ=2mm, L=40cm), the
and the 4′-position of the B-ring was substituted by a hydroxy lower and upper layers of a solvent mixture of CHCl3–MeOH–
group (δCꢀ 158.8).ꢀ Theꢀ absoluteꢀ configurationꢀ atꢀ theꢀ C-2ꢀ posi- H2O–1-PrOH (9:12:8:2) being used as the stationary and mo-
tion was determined to be S from the negative and positive bile phases, respectively. Five-gram fractions were collected
Cotton effects at 304nm and 337nm, respectively, in the CD and numbered according to their order of elution with the mo-
spectrum.
bile phase. HPLC was performed on an ODS column (Inertsil;
Schoepfiajasminꢀ Gꢀ (7): [α]D25 −120, was isolated as an ODS-3, GL Science, Tokyo, Japan; Φ=6mm, L=250mm,
amorphous powder and its elemental composition was de- 1.6mL/min), and the eluate was monitored with a UV detector
termined to be C26H30O13 by HR-ESI-MS. The spectroscopic at 254nm, and a refractive index monitor.
data indicated 7 was a congeneric compound to 5. A highly
Plant Material Branches of S. jasminodora were collect-
deshileded chelated hydroxy proton was observed at δH 11.91 ed in Kunigami Village, Kunigami County, Okinawa, Japan,
1
in the H-NMR spectrum and two aromatic protons on the in July 2006, and a voucher specimen was deposited in the
A-ring were coupled to each other in a meta relationship. The Herbarium of the Faculty of Pharmaceutical Sciences, Gradu-
anomeric carbon chemical shift (δC 97.7) of the glucopyranose ate School of Biomedical and Health Science, Hiroshima Uni-
moiety indicated that this sugar was not directly connected versity (06-SJ-Okinawa-0704).
to a carbon atom, but through an oxygen atom. HMBC cor-
Extraction and Isolation Branches of S. jasminodora
relations H-1″ (δH 5.08) to C-7 (δC 164.9) and H-1‴ (δH 5.31) (13.5kg) were extracted three times with MeOH (45L×3)
to C-2″ (δCꢀ75.7)ꢀconfirmedꢀtheꢀpositionsꢀofꢀsugarꢀlinkagesꢀtoꢀ at room temperature for one week and then concentrated
the aglycone and the terminal apiofuranose to the inner sugar. to 3L in vacuo. The concentrated extract was washed with
Therefore, the structure of 7 was elucidated to be as shown in n-hexane (3L, 35.5g), and then the MeOH layer was concen-
Fig.ꢀ1.ꢀTheꢀabsoluteꢀconfigurationꢀatꢀtheꢀC-2ꢀpositionꢀwasꢀde- trated to a gummy mass. The latter was suspended in water
termined to be R from the positive and negative Cotton effects (3L) and then extracted with EtOAc (3L) to give 53.2g of
at 279nm and 333nm, respectively, in the CD spectrum.17,18)
an EtOAc-soluble fraction. The aqueous layer was extracted
Schoepfiajasminꢀ Hꢀ (8): [α]D22 −75.0, was isolated as a pale with 1-BuOH (3L) to give a 1-BuOH-soluble fraction (146g),
yellow amorphous powder and its elemental composition was and the remaining water-layer was concentrated to furnish
determined to be C26H28O13 by HR-ESI-MS, which was two 28.9g of a water-soluble fraction. The 1-BuOH-soluble frac-
mass units less than that of 7. In the 13C-NMR spectrum, the tionꢀ (145ꢀg)ꢀ wasꢀ subjectedꢀ toꢀ Diaionꢀ HP-20ꢀ CCꢀ (Φ=50mm,
signals for oxygenated methine and methylene carbons, which L=50cm), using a solvent system of H2O–MeOH [(4:1, 6L),
were observed in 7, were replaced by a trisubstituted double (3:2, 6L), (2:3, 6L), and (1:4, 6L)], and MeOH, 1L frac-
bond [δC 105.6 (d), 163.7 (s)], and the oxygenated methine and tions being collected. The residue (9.11g) in fractions 4–8

1140
Vol. 61, No. 11
wasꢀ subjectedꢀ toꢀ silicaꢀ gelꢀ CCꢀ (Φ=3.6cm, L=40cm), using to give 28.5mg of 15 from the peak at 26min. The residue
CHCl3 (1.5L), CHCl3–MeOH [(49:1, 1.5L), (24:1, 1.5L), (1.97g) in fractions 34–44 was separated by ODS open CC
(23:2, 1.5L), (9:1, 3L), (17:3, 1.5L), (4:1, 1.5L), (3:1, 1.5L), andꢀtheꢀresidueꢀ(404ꢀmg)ꢀinꢀfractionsꢀ102–114ꢀwasꢀsubjectedꢀtoꢀ
and (7:3, 1.5L) ], CHCl3–MeOH–H2O (35:15:2, 1.5L), and DCCC to give 20.2mg of 18 in fractions 50–59. The residue
MeOH (1.5L), 250mL fractions being collected. The residue (2.60g) in fractions 45–57 was separated by ODS open CC
(3.34g) in fractions was separated by ODS open CC and andꢀtheꢀresidueꢀ(249ꢀmg)ꢀinꢀfractionsꢀ199–206ꢀwasꢀpurifiedꢀbyꢀ
thenꢀ theꢀ residueꢀ (581ꢀmg)ꢀ inꢀ fractionsꢀ 63–90ꢀ wasꢀ purifiedꢀ byꢀ DCCC.ꢀ Theꢀ residueꢀ (29.8ꢀmg)ꢀ inꢀ fractionsꢀ 40–63ꢀ wasꢀ finallyꢀ
DCCC.ꢀ Theꢀ residueꢀ (202ꢀmg)ꢀ inꢀ fractionsꢀ 37–48ꢀ wasꢀ finallyꢀ purifiedꢀ byꢀ HPLCꢀ (H2O–MeOH, 3:2) to afford 2.01mg of 4
purifiedꢀ byꢀ HPLCꢀ (H2O–MeOH, 4:1) to give 11.8mg of 14, from the peak at 32min.
2.02mg of 13, 21.3mg of 10 and 2.54mg of 9 from the peaks
The residue (10.5g) in fractions 17–20 obtained on Di-
at 19min, 22min, 29min and 32min, respectively. The residue aionꢀ HP-20ꢀ CCꢀ wasꢀ subjectedꢀ toꢀ silicaꢀ gelꢀ CCꢀ (Φ=3.6cm,
(1.09g) in fractions 43–53 obtained on silica gel CC was sepa- L=40cm), using CHCl3 (1.5L), CHCl3–MeOH [(49:1, 1.5L),
rated by ODS open CC and the residue (20.0mg) in fractions (24:1, 1.5L), (23:2, 1.5L), (9:1, 3L), (17:3, 1.5L), (4:1,
31–35ꢀ wasꢀ purifiedꢀ byꢀ DCCCꢀ toꢀ giveꢀ 10.1ꢀmgꢀ ofꢀ 12 in frac- 1.5L), (3:1, 1.5L), and (7:3, 1.5L)], CHCl3–MeOH–H2O
tions 71–86. The residue (132mg) in fractions 60–74 was puri- (35:15:2, 1.5L), and MeOH (1.5L), 250mL fractions being
fiedꢀbyꢀDCCCꢀandꢀtheꢀprecipitateꢀ(8.23ꢀmg)ꢀinꢀfractionsꢀ33–38ꢀ collected. The soluble residue (1.51g) in fractions 26–36 was
wasꢀpurifiedꢀbyꢀHPLCꢀ(H2O–MeOH, 4:1) to give 2.82mg of separated by ODS Open CC and the residue (880mg) was
11 from the peak at 14min.
purifiedꢀbyꢀDCCC.ꢀTheꢀresidueꢀ(50ꢀmgꢀoutꢀofꢀ147ꢀmg)ꢀinꢀfrac-
Theꢀ residueꢀ (14.7ꢀg)ꢀ inꢀ fractionsꢀ 9‒13ꢀ obtainedꢀ onꢀ Di- tionsꢀ 117–144ꢀ wasꢀ finallyꢀ purifiedꢀ byꢀ HPLCꢀ toꢀ giveꢀ 11.2ꢀmgꢀ
aionꢀ HP-20ꢀ CCꢀ wasꢀ subjectedꢀ toꢀ silicaꢀ gelꢀ CCꢀ (Φ=5.5cm, of 16 and 4.58mg of 17 from the peaks at 41min and 49min,
L=46cm), using CHCl3 (3L), CHCl3–MeOH [(49:1, 3L), respectively. The precipitate (100mg out of 687mg) obtained
(24:1, 3L), (23:2, 3L), (9:1, 3L), (17:3, 3L), (4:1, 3L), (3:1, inꢀfractionsꢀ26–36ꢀwasꢀpurifiedꢀbyꢀHPLCꢀ(H2O–MeOH, 3:2)
3L), (7:3, 3L) (3:2. 3L), and (1:1, 3L)], CHCl3–MeOH–H2O to give 26.3mg of 19 and 3.00mg of 22 from the peaks at
(25:25:2, 3L), and MeOH (3L), 500mL fractions being col- 34min and 42min, respectively. The residue (1.31g) in frac-
lected. The residue (2.91g) in fractions 29–42 was separated tions 37–46 was separated by ODS open CC, and the residue
by ODS open CC to give two residues, 539mg in fractions (127ꢀmg)ꢀ wasꢀ subjectedꢀ toꢀ DCCCꢀ toꢀ yieldꢀ 42.9ꢀmgꢀ ofꢀ 1 and
73–108 and 987mg in fractions 125–164. The former residue 23mg of 7 in fractions 42–62 and 65–82, respectively. The
wasꢀ purifiedꢀ DCCCꢀ andꢀ theꢀ residueꢀ (70.0ꢀmg)ꢀ inꢀ fractionsꢀ residue (168mg) in fractions 211–220 was separated by DCCC
57–62ꢀ wasꢀ purifiedꢀ againꢀ byꢀ HPLCꢀ (H2O–MeOH, 7:3) to andꢀ theꢀ residueꢀ (22.3ꢀmg)ꢀ inꢀ fractionsꢀ 120–143ꢀ wasꢀ purifiedꢀ
give a residue (14.0mg) from the peak at 12min. The residue by HPLC (H2O–MeOH, 11:9) to afford 2.40mg of 9 from the
wasꢀ furtherꢀ purifiedꢀ byꢀ HPLCꢀ (Cosmosil;ꢀ Cholester,ꢀ Na- peak at 25min.
kalai Tesque, Kyoto, Japan; Φ=10mm, L=250mm, 1.6mL/
Schoepfiajasminꢀ Aꢀ (1): Amorphous powder, [α]D25 −19.7
min) (H2O–MeOH, 7:3) to give 1.0mg of 6 from the peak (c=0.99, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3367, 2932, 1619, 1499,
at 35min. The latter residue was separated by DCCC and the 1446, 1261, 1078, 821; UV λmax (MeOH) nm (logε): 319 (3.81),
1
residueꢀ (271ꢀmg)ꢀ wasꢀ purifiedꢀ byꢀ HPLCꢀ (H2O–MeOH, 3:2) 278 (3.96), 217 (4.14); H-NMR (600MHz, DMSO-d6, 95°C) δ:
to afford 34.1mg of 5 and 27.4mg of 20 from the peaks at 13.13 (1H, s, 2′-OH), 7.73 (1H, d, J=8.9Hz, H-6′), 7.26 (4H,
12min and 14min, respectively. The residue (3.20g) in frac- m, J=5.8Hz, H-2, 3, 5, 6), 7.16 (1H, tt, J=5.8, 2.8Hz, H-4),
tions 43–53 was separated by ODS open CC and the residue 6.39 (1H, d, J=8.9Hz, H-5′), 5.18 (1H, d, J=1.0Hz, H-1‴),
(184ꢀmg)ꢀ inꢀ fractionsꢀ 71–76ꢀ wasꢀ purifiedꢀ byꢀ DCCC.ꢀ Theꢀ 4.72 (1H, d, J=9.6Hz, H-1″), 4.14 (1H, brt, J=9.0Hz, H-2″),
residueꢀ (129ꢀmg)ꢀ inꢀ fractionsꢀ 25–36ꢀ wasꢀ finallyꢀ purifiedꢀ byꢀ 3.68 (1H, dd, J=11.7, 2.4Hz, H-6″a), 3.58 (1H, d, J=1.0Hz,
HPLC (H2O–MeOH, 7:3) to afford 29.1mg of 2 from the H-2‴), 3.49 (1H, dd, J=11.7, 5.5Hz, H-6″b), 3.43 (1H, dd,
peak at 52min. The residue (2.58g) in fractions 54–68 was J=8.6, 8.6Hz, H-3″), 3.25 (1H, dd, J=8.9, 8.6Hz, H-4″), 3.24
separated by ODS open CC and the residue (215mg) in frac- (2H, t, J=7.2Hz, H2-α), 3.21 (1H, ddd, J=8.9, 5.5, 2.4Hz,
tionsꢀ 77–95ꢀ wasꢀ purifiedꢀ byꢀ DCCC.ꢀ Theꢀ residueꢀ (30.2ꢀmg)ꢀ inꢀ H-5″), 3.15 (1H, d, J=11.3Hz, H-5‴a), 3.12 (1H, d, J=9.3Hz,
fractionsꢀ59–66ꢀwasꢀfinallyꢀpurifiedꢀbyꢀHPLCꢀtoꢀyieldꢀ8.19ꢀmgꢀ H-4‴a), 3.01 (1H, d, J=11.3Hz, H-5‴b), 2.96 (2H, t, J=7.2Hz,
of 21 from the peak at 44min. The residue (2.58g) in frac- H2-β), 2.62 (1H, d, J=9.3Hz, H-4‴b); 13C-NMR (150MHz,
tions 54–57 was separated by ODS open CC and the residue DMSO-d6, 95°C): Table 1; HR-ESI-MS (positive-ion mode)
(133ꢀmg)ꢀ inꢀ fractionsꢀ 174–190ꢀ wasꢀ purifiedꢀ byꢀ DCCC.ꢀ Theꢀ m/z: 559.1785 [M+Na]+ (Calcd for C26H32O12Na: 559.1786).
residueꢀ (19.7ꢀmg)ꢀ inꢀ fractionsꢀ 24–28ꢀ wasꢀ finallyꢀ purifiedꢀ byꢀ
HPLC (H2O–MeOH, 3:2) to give 4.05mg of 3 from the peak (c=1.04, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3356, 2934, 1615, 1513,
at 16min. 1446, 1362, 1257, 1081, 998, 825; UV λmax (MeOH) nm (logε):
Schoepfiajasminꢀ Bꢀ (2): Amorphous powder, [α]D25 −21.7
1
The residue (10.5g) in fractions 14–16 obtained on Di- 317 (3.72), 276 (3.90), 217 (4.07); H-NMR (600MHz, DMSO-
aionꢀ HP-20ꢀ CCꢀ wasꢀ subjectedꢀ toꢀ silicaꢀ gelꢀ CCꢀ (Φ=3.6cm, d6, 95°C) δ: 13.15 (1H, s, 2′-OH), 8.82 (1H, s, 4-OH), 7.70 (1H,
L=50cm), using CHCl3 (1.5L), CHCl3–MeOH [(49:1, 1.5L), d, J=8.9Hz, H-6′), 7.02 (2H, d, J=8.3Hz, H-2, 6), 6.66 (2H,
(24:1, 1.5L), (23:2, 1.5L), (9:1, 3L), (17:3, 1.5L), (4:1, d, J=8.3Hz, H-3, 5), 6.38 (1H, d, J=8.9Hz, H-5′), 5.17 (1H,
1.5L), (3:1, 1.5L), and (7:3, 1.5L)], CHCl3–MeOH–H2O brs, H-1‴), 4.73 (1H, d, J=9.6Hz, H-1″), 4.10 (1H, m, H-2″),
(35:15:2, 1.5L), and MeOH (1.5L), 250mL fractions being 3.68 (1H, dd, J=11.7, 2.1Hz, H-6″a), 3.59 (1H, brs, H-2‴), 3.50
collected. The residue (743mg) in fractions 24–33 was sepa- (1H, dd, J=11.7, 5.5Hz, H-6″b), 3.43 (1H, dd, J=8.9, 8.9Hz,
rated by ODS open CC and the residue (230mg) in fractions H-3″), 3.26 (1H, dd, J=8.9, 8.9Hz, H-4″), 3.21 (1H, ddd,
127–138ꢀ wasꢀ subjectedꢀ toꢀ DCCC.ꢀ Theꢀ residueꢀ (70ꢀmg)ꢀ inꢀ J=8.9, 5.5, 2.1Hz, H-5″), 3.13 (2H, t, J=7.2Hz, H2-α), 3.16
fractionsꢀ 35–40ꢀ wasꢀ purifiedꢀ byꢀ HPLCꢀ (H2O–MeOH, 13:7) (1H, d, J=11.0Hz, H-5‴a), 3.12 (1H, d, J=9.3Hz, H-4‴a), 3.04

November 2013
1141
(1H, d, J=11.0Hz, H-5‴b), 2.84 (2H, t, J=6.8Hz, H2-β), 2.64 d, J=9.8Hz, H-1′), 4.07 (1H, dd, J=9.8, 8.7Hz, H-2′), 3.82
(1H, d, J=9.3Hz, H-4‴b); 13C-NMR (150MHz, DMSO-d6, (1H, dd, J=12.0, 1.6Hz, H-6′a), 3.70 (1H, dd, J=12.0, 5.1Hz,
95°C): Table 1; HR-ESI-MS (positive-ion mode) m/z: 575.1729 H-6′b), 3.41 (1H, dd, J=9.2, 8.7Hz, H-3′), 3.36 (1H, ddd,
[M+Na]+ (Calcd for C26H32O13Na: 575.1735).
J=9.1, 5.1, 1.6Hz, H-5′), 3.34 (1H, brdd, J=9.0, 9.0Hz, H-4′),
Schoepfiajasminꢀ Cꢀ (3): Amorphous powder, [α]D26 −32.6 2.97 (1H, dd, J=16.9, 12.5Hz, H-3a), 2.72 (1H, dd, J=16.9,
(c=0.23, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3394, 2930, 1618, 1502, 3.0Hz, H-3b); 13C-NMR (150MHz, CD3OD, 35°C): Table
1454, 1360, 1272, 1079, 1023, 899; UV λmax (MeOH) nm 2;ꢀ CDꢀ Δε (nm): +1.12 (337), −0.78 (304) (c=4.80×10−5 M,
1
(logε): 316 (3.85), 277 (4.03), 218 (4.14); H-NMR (400MHz, MeOH); HR-ESI-MS (positive-ion mode) m/z: 441.1156 [M+
CD3OD, 35°C) δ: 7.72 (1H, d, J=8.8Hz, H-6′), 7.06 (1H, dd, Na]+ (Calcd for C21H22O9Na: 441.1156).
J=7.9, 7.9Hz, H-5), 6.70 (1H, dd-like, J=7.9, 2.4Hz, H-6), 6.68
Schoepfiajasminꢀ Gꢀ (7): Amorphous powder, [α]D25 −120
(1H, t-like, J=2.4Hz, H-2), 6.59 (1H, ddd, J=7.9, 2.4, 2.4Hz, (c=0.02); IR νmaxꢀ (film)ꢀ cm−1: 3394, 2934, 1644, 1577, 1449,
H-4), 6.40 (1H, d, J=8.8Hz, H-5′), 5.30 (1H, d, J=0.7Hz, 1375, 1297, 1085, 1027, 829; UV λmax (MeOH) nm (logε): 321
1
H-1‴), 4.92 (1H, d, J=9.0Hz, H-1″), 4.48 (1H, m, H-2″), 3.85 (3.66), 280 (4.09), 220 (4.17); H-NMR (600MHz, DMSO-d6,
(1H, dd, J=12.0, 2.0Hz, H-6″a), 3.76 (1H, d, J=0.7Hz, H-2‴), 35°C) δ: 11.91 (1H, s, 5-OH), 7.52 (2H, d, J=7.5Hz, H-2′, 6′),
3.70 (1H, dd, J=12.0, 4.9Hz, H-6″b), 3.58 (1H, dd, J=9.2, 7.41 (3H, m, H-3′, 4′, 5′), 6.18 (1H, d, J=2.1Hz, H-8), 6.13
9.2Hz, H-3″), 3.45 (1H, dd, J=9.7, 9.2Hz, H-4″), 3.36 (1H, d, (1H, d, J=2.1Hz, H-6), 5.63 (1H, dd, J=12.6, 2.9Hz, H-2),
J=11.1Hz, H-5‴a), 3.35 (1H, ddd, J=9.7, 4.9, 2.0Hz, H-5″), 5.31 (1H, d, J=1.3Hz, H-1‴), 5.08 (1H, d, J=7.1Hz, H-1″),
3.22 (2H, t, J=7.8Hz, H2-α), 3.17 (1H, d, J=11.1Hz, H-5‴b), 3.85 (1H, d, J=9.5Hz, H-4‴a), 3.77 (1H, d, J=1.3Hz, H-2‴),
3.15 (1H, d, J=9.6Hz, H-4‴a), 2.94 (2H, t, J=7.8Hz, H2-β), 3.70 (1H, dd, J=12.0, 2.3Hz, H-6″a), 3.62 (1H, d, J=9.5Hz,
2.58 (1H, d, J=9.6Hz, H-4‴b); 13C-NMR (100MHz, CD3OD, H-4‴b), 3.49 (1H, dd, J=8.9, 7.1Hz, H-2″), 3.45 (1H, dd,
35°C): Table 1; HR-ESI-MS (positive-ion mode) m/z: 575.1733 J=8.9, 8.5Hz, H-3″), 3.48 (1H, dd, J=12.0, 5.2Hz, H-6″b), 3.37
[M+Na]+ (Calcd for C26H32O13Na: 575.1735).
(1H, ddd, J=9.6, 5.2, 2.3Hz, H-5″), 3.35 (1H, d, J=11.6Hz,
Schoepfiajasminꢀ Dꢀ (4): Amorphous powder, [α]D22 −86.0 H-5‴a), 3.33 (1H, d, J=11.6Hz, H-5‴b), 3.27 (1H, dd, J=17.2,
(c=0.10, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3356, 2923, 1622, 1493, 12.4Hz, H-3ax), 3.23 (1H, dd, J=9.6, 8.5Hz, H-4″), 2.84 (1H,
1431, 1370, 1275, 1177, 1075, 829; UV λmax (MeOH) nm (logε): dd, J=17.2, 2.9Hz, H-3eq); 13C-NMR (150MHz, DMSO-
1
307 (3.97), 275 (4.30), 221 (4.29); H-NMR (400MHz, DMSO- d6,ꢀ 35°C):ꢀ Tableꢀ 2;ꢀ CDꢀ Δε (nm): −1.41 (333), +1.51 (279)
d6, 95°C) δ: 7.23 (4H, m, H-2, 3, 5, 6), 7.14 (1H, m, H-4), 6.39 (c=4.60×10−5 M, MeOH); HR-ESI-MS (positive-ion mode)
(1H, d, J=2.0Hz, H-3′), 6.17 (1H, d, J=2.0Hz, H-5′), 5.00 m/z: 573.1576 [M+Na]+ (Calcd for C26H30O13Na: 573.1579).
(1H, d, J=7.7Hz, H-1″), 4.94 (1H, d, J=7.4Hz, H-1‴), 3.70
SchoepfiajasminꢀHꢀ(8): Pale yellow amorphous powder, [α]D22
(1H, dd, J=11.7, 2.0Hz, H-6″a), 3.70 (1H, dd, J=11.8, 1.9Hz, −75.0 (c=0.20, C5H5N); IR νmaxꢀ(film)ꢀcm−1: 3395, 2928, 1664,
H-6‴a), 3.50 (1H, dd, J=11.7, 6.5Hz, H-6″b), 3.50 (1H, dd, 1613, 1452, 1349, 1302, 1077, 1041, 821; UV λmax (MeOH) nm
1
J=11.8, 6.4Hz, H-6‴b), 3.45 (2H, t, J=7.4Hz, H2-α), 3.42 (logε): 346 (4.03), 260 (4.55), 219 (4.45); H-NMR (600MHz,
(1H, brt, J=9.0Hz, H-3″), 3.42 (1H, brt, J=9.0Hz, H-3‴), 3.32 DMSO-d6, 35°C) δ: 12.63 (1H, s, 5-OH), 8.10 (2H, dd, J=8.1,
(4H, m, H-2”, 5”, 2‴, 5‴), 3.18 (2H, m, H-4″, 4‴), 2.93 (2H, t, 1.6Hz, H-2′, 6′), 7.60 (3H, m, H-3′, 4′, 5′), 7.04 (1H, s, H-3),
J=7.4Hz, H2-β); 13C-NMR (100MHz, DMSO-d6, 95°C): Table 6.86 (1H, d, J=2.2Hz, H-6), 6.46 (1H, d, J=2.2Hz, H-8), 5.35
1; HR-ESI-MS (positive-ion mode) m/z: 605.1847 [M+Na]+ (1H, d, J=1.5Hz, H-1‴), 5.18 (1H, d, J=7.1Hz, H-1″), 3.91 (1H,
(Calcd for C27H34O14Na: 605.1841).
d, J=9.3Hz, H-4‴a), 3.78 (1H, d, J=1.5Hz, H-2‴), 3.74 (1H,
Schoepfiajasminꢀ Eꢀ (5): Amorphous powder, [α]D26 +45.7 brd, J=11.8Hz, H-6″a), 3.66 (1H, d, J=9.3Hz, H-4‴b), 3.56
(c=1.91, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3441, 2933, 1674, 1594, (1H, dd, J=8.9, 7.0Hz, H-2″), 3.53 (1H, m, H-5″), 3.50 (1H, br
1448, 1366, 1266, 1109, 1022, 891; UV λmax (MeOH) nm t, J=9.0Hz, H-3″), 3.50 (1H, brd, J=11.8Hz, H-6″b), 3.36 (1H,
1
(logε): 310 (3.85), 278 (4.02), 216 (4.22); H-NMR (400MHz, d, J=11.3Hz, H-5‴a), 3.34 (1H, d, J=11.3Hz, H-5‴b), 3.25
CD3OD, 95°C) δ: 7.73 (1H, d, J=8.6Hz, H-5), 7.54 (2H, dd, (1H, dd, J=8.9, 8.2Hz, H-4″); 13C-NMR (150MHz, DMSO-d6,
J=7.0, 1.4Hz, H-2′, 6′), 7.41 (2H, dd, J=7.3, 7.0Hz, H-3′, 5′), 35°C): Table 2; HR-ESI-MS (positive-ion mode) m/z: 571.1420
7.34 (1H, tt, J=7.3, 1.4Hz, H-4′), 6.57 (1H, d, J=8.6Hz, H-6), [M+Na]+ (Calcd for C26H28O13Na: 571.1422).
5.51 (1H, dd, J=12.8, 3.1Hz, H-2), 4.92 (1H, d, J=9.5Hz,
Acid Hydrolysis of Schoepfiajasmin A (1) to Schoepfin
H-1″), 4.08 (1H, brdd, J=9.5, 9.5Hz, H-2″), 3.86 (1H, dd, B (16)ꢀ ꢀSchoepfiajasminꢀ Aꢀ (1) (9.2mg) was hydrolyzed with
J=11.7, 1.7Hz, H-6″a), 3.83 (1H, ddd, J=9.0, 4.5, 1.7Hz, H-5″), 1mL of 5% H2SO4 at 80°C for 1h and then the reaction mix-
3.67 (1H, dd, J=11.7, 4.5Hz, H-6″b), 3.40 (1H, dd, J=9.5, ture was neutralized by the addition of Amberlite IRA96SB.
9.0Hz, H-3″), 3.34 (1H, brt, J=9.0Hz, H-4″), 3.00 (1H, dd, The aqueous layer was partitioned with an equal amount of
J=16.8, 3.1Hz. H-3eq), 2.84 (1H, dd, J=16.8, 12.8Hz, H-3ax); 1-BuOH and then evaporation of the 1-BuOH layer left 6.3mg
13C-NMR (100MHz, CD3OD,ꢀ 35°C):ꢀ Tableꢀ 2;ꢀ CDꢀ Δε (nm): ofꢀschoepfinꢀBꢀ(16).
−0.86 (334), +3.05 (301) (c=2.70×10−5 M, MeOH); HR-ESI-
SchoepfinꢀBꢀ(16): Amorphous powder, [α]D25 +20.2 (c=0.63,
1
MS (positive-ion mode) m/z: 425.1207 [M+Na]+ (Calcd for MeOH); H- and 13C-NMR: essentially the same as those re-
C21H22O8Na: 425.1207).
Schoepfiajasminꢀ Fꢀ (6): Amorphous powder, [α]D25 +28.0 m/z: 427.1362 [M+Na]+ (Calcd for C21H24O8Na: 427.1363).
(c=0.10, MeOH); IR νmaxꢀ(film)ꢀcm−1: 3449, 2922, 1637, 1559,
Sugar Analysis About 500µg of each compound, 1–4, 7
portedꢀforꢀschoepfinꢀBꢀ(16)11); HR-ESI-MS (positive-ion mode)
1450, 1359, 1262, 1074, 835; UV λmax (MeOH) nm (logε): 312 and 8, was hydrolyzed with 1M HCl (0.1mL) at 90°C for 2h.
(3.92), 274 (4.13), 229 (4.40); 1H-NMR (600MHz, CD3OD, The reaction mixtures were partitioned with an equal amount
35°C) δ: 7.71 (1H, d, J=8.9Hz, H-5), 7.40 (2H, d, J=8.5Hz, of EtOAc (0.1mL), and the water layers were analyzed with
H-2′, 6′), 6.81 (2H, d, J=8.5Hz, H-3′, 5′), 6.51 (1H, d, a chiral detector (JASCO OR-2090plus) on an amino column
J=8.9Hz, H-6), 5.43 (1H, dd, J=12.5, 3.0Hz, H-2), 4.90 (1H, [Asahipak NH2P-50 4E, CH3CN–H2O (4:1), 1mL/min]. The

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Vol. 61, No. 11
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hydrolyzates of 1–3 each gave a peak for D-apiose at 6.1min,
that of 4 a peak for D-glucose at 19.4min, and those of 7 and
8 peaks for D-apiose at 6.1min and D-glucose at 19.4min, with
positiveꢀ opticalꢀ rotationꢀ signs.ꢀ Theꢀ peaksꢀ wereꢀ identifiedꢀ byꢀ
co-chromatography with authentic samples.
Acknowledgments The authors are grateful for access to
the superconducting NMR instrument (JEOL JNM α-400) at
the Analytical Center of Molecular Medicine of the Hiroshima
University Faculty of Medicine, and the LTQ Orbitrap XL
HR-ESI-MS and the superconducting NMR instrument (JEOL
ECA-600) at the Natural Science Center for Basic Research
and Development (N-BARD), Hiroshima University. This
work was supported in part by Grants-in-Aid from the Min-
istry of Education, Culture, Sports, Science and Technology
of Japan (Nos. 22590006 and 23590130), the Japan Society for
the Promotion of Science, and the Ministry of Health, Labour
and Welfare. Thanks are also due to the Research Foundation
for Pharmaceutical Sciences and the Takeda Science Founda-
tionꢀforꢀtheꢀfinancialꢀsupport.
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