Four new norlignan glycoside isomers from the twigs of Cephalotaxus oliveri Mast.

Article abstract of DOI:10.1016/j.tetasy.2017.10.017

Four novel isomers of norlignan glycoside were isolated from Cephalotaxus oliveri Mast. Their structures were elucidated as 3S-4″-O-β-D-glucopyranosylnyasol 1, 3S-4′-O-β-D-glucopyranosylnyasol 2, 3S-4″-O-β-D-glucopyranosylhinokiresinol 3, 3S-4′-O-β-D-gluc

Full text of DOI:10.1016/j.tetasy.2017.10.017

Tetrahedron: Asymmetry 28 (2017) 1686–1689
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Four new norlignan glycoside isomers from the twigs
of Cephalotaxus oliveri Mast.
Fan-Cheng Meng , Hui Liu a,b, Xiao-Jun Huang a,b, Yu Chang , Dai Ren , Li-Gen Lin , Qing-Qian Zeng ,
Qing-Wen Zhang
a
a
a
a
a
c
a,
⇑
State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macao
JNU-HKUST Joint Laboratory for Neuroscience & Innovative Drug Research, Jinan University, Guangzhou 510632, PR China
Guangdong Research Institute of Traditional Chinese Medicine, Guangzhou 510520, PR China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 July 2017
Revised 4 October 2017
Accepted 11 October 2017
Available online 16 November 2017
Four novel isomers of norlignan glycoside were isolated from Cephalotaxus oliveri Mast.. Their structures
00
0
00
were elucidated as 3S-4 -O-b-
D
-glucopyranosylnyasol 1, 3S-4 -O-b-
D
-glucopyranosylnyasol 2, 3S-4 -O-b-
0
D
-glucopyranosylhinokiresinol 3, 3S-4 -O-b-
D-glucopyranosylhinokiresinol 4 by extensive spectroscopic
1
13
1
1
methods including 1D and 2D NMR experiments ( H, C, DEPT, H– H COSY, HSQC, HMBC, ROESY) along
with HR-ESIMS and comparison to literature data. Their absolute configurations were elucidated through
CD spectra coupled with the quantum chemical CD calculations.
Ó 2017 Elsevier Ltd. All rights reserved.
1
. Introduction
Cephalotaxus oliveri Mast. (Cephalotaxaceae) is mainly dis-
2. Results and discussion
The molecular formula of compound 1 was determined to be
tributed in Vietnam, and the Southeast and Southwest regions of
China. Phytochemical investigations showed that alkaloids includ-
C
+NH
calcd for C23
23
H
26
O
7
in agreement with its HR-ESIMS data (m/z 432.2003 [M
1
+
ꢀ
4
] , calcd for C23
H
30
O
7
N 432.2022 and m/z 413.1585 [MꢀH] ,
1
ing cephalotaxine type and homoerythrina type alkaloids were the
main constituents of Cephalotaxus genus. Lactones, flavonoids,
essential oil and other natural compounds were also found from
C. oliveri and other plants of Cephalotaxus genus.2 Recent studies
have revealed that the bioactive components from Cephalotaxus-
genus have pharmacological activities, such as anti-tumor, anti-
25
H O
7
413.1600). The H NMR spectrum of 1 showed
the signals of two para-disubstituted aromatic rings [d 7.11 (d,
2H, J = 8.5 Hz), 7.04 (d, 2H, J = 8.7 Hz); 7.14 (d, 2H, J = 8.7 Hz),
6.73 (d, 2H, J = 8.5 Hz)] and those of a vinyl group [d 5.12 (br d,
1H, J = 16.7 Hz), 5.12 (br d, 1H, J = 10.8 Hz) and 6.01 (ddd, 1H, J =
16.7, 10.8, 6.1 Hz)] and a vinylene (d 6.49, d, 1H, J = 11.4 Hz; 5.65,
dd, 1H, J = 11.4, 9.7 Hz). The signals at d 6.01 and 5.65 are further
coupled with a hydrogen at d 4.50 (dd, 1H, J = 9.7, 6.4 Hz), which
indicated the existence of a 1,4-pentadiene group. The 1,4-pentadi-
ene 1,3-disubstituted by two para-disubstituted aromatic rings
were confirmed by the correlation between the hydrogen at d
4.50 (dd, 1H, J = 9.7, 6.1 Hz) and a quaternary carbon at d 138.8,
and the correlation between the hydrogen at d 6.49 (d, 1H,
J = 11.4 Hz) and a quaternary carbon at d 129.8 in the HMBC spec-
trum. Due to the coupling constant between H-1 and H-2 (J = 11.4
Hz), the configuration of the double bond was determined as Z. A
–5
5
–11
oxidant, anti-inflammatory, and anti-phytoviral activities.
Some cephalotaxine type alkaloids, such as homoharringtonine,
showed potent anti-cancer activity. Homoharringtonine had been
approved by the Food and Drug Administration of USA for the
treatment of chronic myeloid leukemia in the chronic phase or
accelerated phase.
Herein, we report the isolation of four new norlignan glycoside
isomers from C. oliveri. Their structures were elucidated by exten-
sive spectroscopic methods including 1D and 2D NMR experiments
1
13
1
1
(
H, C, DEPT, H– H COSY, ROESY, HSQC, HMBC) along with
1
3
HR-ESIMS and comparison of CD spectra with quantum chemical
calculated CD spectra.
doublet at d 4.88 (d, 1H, J = 7.4 Hz) whose C NMR signals at d
102.3, indicated the existence of a b-glucopyranosyl. Based on
the information above, compound 1 was deduced to be a glucoside
of nyasol. The glycosidic linkage is hard to determine by HMBC due
0
00
to the very closely chemical shifts of C-4 and C-4 (d 157.7 and
57.6). However, the correlation between the anomeric hydrogen
1
⇑
Corresponding author at: Tel.: +853 8822 4879; fax: +853 2884 1358.
E-mail address: qwzhang@umac.mo (Q.-W. Zhang).
0
0
00
of the glucopyranosyl and the H-3 , 5 could be observed in the
https://doi.org/10.1016/j.tetasy.2017.10.017
957-4166/Ó 2017 Elsevier Ltd. All rights reserved.
0

F.-C. Meng et al. / Tetrahedron: Asymmetry 28 (2017) 1686–1689
1687
ROSEY spectrum, which suggested that the glucopyranosyl should
31+G(d)] computations, respectively. The predicted CD spectra of
ZS and ES revealed good agreement with the experimental ones
of 1, 2 (Fig. 2A) and 3, 4 (Fig. 2B), respectively. Therefore, the abso-
lute configurations of 1, 2 and 3, 4 were, respectively, established
00
be substituted at C-4 . Its absolute configuration was determined
as -glycopyranosyl by HPLC analysis of the derivative of its acid
hydrolyzed residue.
D
1
2
These data indicated that compound 1
0
0
had the same planar structure as mononyasine A (4 -O-b-
D
-
as (1Z,3S) and (1E,3S). Consequently, these four norlignan glycoside
glucopyranosylnyasol).13
isomers were elucidated as 3S-4 -O-b-
00
D
-glucopyranosylnyasol 1,
0
00
Compound 2 gave a same molecular formula C23
H
26
O
7
from its
] , calcd for C23
413.1600).
3S-4 -O-b-
D
-glucopyranosylnyasol 2, 3S-4 -O-b-
hinokiresinol 3, 3S-4 -O-b-D-glucopyranosylhinokiresinol 4.
D
-glucopyranosyl-
+
0
HR-ESIMS spectrum (m/z 432.2002 [M+NH
4
H
30
O
7
N
ꢀ
4
32.2022 and m/z 413.1587 [MꢀH] , calcd for C23
H
25
O
7
The isolation and planar structures of mononyasines A and B
1
13
13
When comparing the H and C NMR spectra of 2 and 1, they give
similar NMR data, which indicates that compound 2 was the iso-
meric compound of compound 1. In the ROSEY spectrum of com-
pound 2, the correlation between the anomeric hydrogen of the
were reported in 1989. However, the absolute configurations of
mononyasines A and B have not been determined until now. Com-
pounds 1 and 2 share the same planar structures as mononyasines
A and B, but have opposite specific rotation values. Compounds 1
0
0
glucopyranosyl and the H-3 , 5 indicated that the glucopyranosyl
0
was substituted at C-4 . Compound 2 had the same planar structure
1
3
as mononyasine B.
Compounds 3 and 4 also gave the same molecular formula,
, in their HR-ESIMS spectrum. Their NMR data were also
Exptl of 1
2
1
0
0
0
Exptl of 2
Calcd of ZS-aglycone
Calcd of ZR-aglycone
23 26 7
C H O
similar to those of compounds 1 and 2, except that the coupling
constants between H-1 and H-2 were 15.9 Hz, which indicated that
they were the glycosides of hinokiresinol, a pair of E-isomers of
compounds 1 and 2. The attachments of glycopyranosyl moiety
00
0
of compounds 3 to C-4 , and to C-4 for compound 4, were indi-
cated by the HMBC correlations of H-glu-1 to the corresponding
carbon, respectively. The glycopyranosyl moieties were also deter-
mined as having a D-configuration by HPLC analysis of the deriva-
tives of their acid hydrolyzed residues.
-
10
20
-
Herein, the absolute configurations of 1–4 were determined by
the CD spectra coupled with the quantum chemical CD calculations
in Gaussian 09 software and comparison of their physicochemical
properties. Four absolute configurations (ZS/ZR and ES/ER) of agly-
cone were selected randomly for the systematically conforma-
tional analysis in the SYBYL 8.1 program by using MMFF94’s
molecular force field. Among the obtained conformers, eight and
ten lowest-energy conformers were selected for optimization and
further time-dependent DFT [CAM-B3LYP/6-31 + G(d)//B3LYP/6-
2
00
250
300
350
400
wavelength (nm)
A
5
Exptl of 3
Exptl of 4
Calcd of ES-aglycone
Calcd of ER-aglycone
0
D
HO
HO
1'
O
O
1
2
HO
HO
4
3
OH
5
-5
2
00
250
300
350
400
1"
wavelength (nm)
HO
B
O
HO
HO
O
5
0
5
OH
Exptl of ES-aglycone
Cacld of ES-aglycone
OH
1
2
HO
HO
O
HO
HO
O
OH
HO
O
HO
HO
O
OH
-
OH
200
250
300
350
400
3
4
Wavelength (nm)
C
1
1
HMBC
ꢀ
H- H COSY
ROESY
Figure 1. Structures of compounds 1–4 and their key 1H– H COSY, HMBC and
ROESY correlations.
1
Figure 2. Calculated and experimental CD spectra of compounds 1,
compounds 3, 4 (B) and reference (3S)-hinokiresinol (C).
2
(A),

1
688
F.-C. Meng et al. / Tetrahedron: Asymmetry 28 (2017) 1686–1689
and 2 are the epimers of mononyasines A and B, respectively. Thus,
mononyasines A and B would have a (3R)-configuration. The agly-
cones of compounds 1–4, naysol and hinokiresinol, have been iso-
lated and their enantioselective synthesis were also achieved.
There are no ambiguities in the assignment of the absolute config-
Spectrometer with KBr pellets (PerkinElmer, Waltham, USA). Opti-
cal rotations were measured on PerkinElmer Model 341
polarimeter at the sodium D line at 20.0 °C (PerkinElmer, Waltham,
USA). UV spectra were obtained on a HACH DR-6000 UV/VIS spec-
trophotometer (HACH, Loveland, USA). 1D and 2D NMR spectra
a
1
4–16
uration of (ꢀ)- and (+)-nyasol. It was reported that synthetic (+)-
3
were recorded on a Bruker Ascend 600 spectrometer (CD OD used
14
nyasol has an (S)-stereogenic center and (ꢀ)-nyasol has an (R)-
as solvent and TMS as an internal standard, Fallanden, Switzer-
land). HPLC was performed on an Agilent 1200 Chromatograph
equipped with a 250 mm ꢁ 4.6 mm i.d. Cosmosil 5C18-AR-II col-
umn (Nacalai Tesque Inc., Kyoto, Japan) at 25 °C. Column chro-
matography was performed on silica gel (200–300 mesh,
Qingdao Marine Chemical Group Co., Qingdao, China) and Sepha-
dex LH-20 (Pharmacia, USA); the solvents of analytical grade used
for extraction and gel chromatography were supplied by Kaitong
Chemical Co. Ltd. (Tianjin, China). Solvents applied for preparative
column and HPLC analysis were of HPLC grade and purchased from
Merck (Darmstadt, Germany). Distilled water was purified with a
Millipore Milli Q-Plus system (Millipore, Milford, MA, USA). (3S)-
Hinokiresinol was purchased from Shanghai Yihe Biological Tech-
nology Co., Ltd. (Shanghai, China).
1
5
17
stereogenic center. Their CD data were also reported. However,
the reports about the absolute configuration determination of
hinokiresinol were often contradictory.1
7–19
Hinokiresinol was first
reported from Chamaecyparis obtusa by Hirose et al.20 A (3S)-con-
figuration was reported by chemical transformation. Minami
21
1
7
et al. claimed a (3S)-configuration for (ꢀ)-hinokiresinol followed
1
8
by Lassen et al. who synthesized the hinokiresinol racemates and
then separated them on a chiral column. Lassen et al. assigned (3S)
and (3R) for (ꢀ) and (+)-hinokiresinol, respectively. The synthe-
sized (R)-hinokiresinol by Hamilton et al.16 had a negative specific
rotation. Commercial (3S)-hinokiresinol exhibited a positive speci-
2
0
fic rotation {[
D
a] = +3.5, (c 1.2, acetone)} and its CD spectrum was
in good agreement with the predicted one (Fig. 2C), which sup-
1
6
ported Hamilton’s result.
. Conclusion
4
.2. Plant material
3
The twigs of Cephalotaxus oliveri Mast. were collected in Jiujiang,
Jiangxi province, China in April 2014, and authenticated by Profes-
sor Qing-Qian Zeng (Guangdong Research Institute of Traditional
Chinese Medicine). A voucher specimen was deposited in the
Guangdong Research Institute of Traditional Chinese Medicine.
A chemical investigation on the twigs of Cephalotaxus oliveri
Mast. led to the isolation of four new norlignan glycosides 1–4
Fig. 1). Compounds 1 and 2 are epimers of mononyasine A and
mononyasine B, respectively. Compounds 3 and 4 are the E-iso-
mers of compounds 1 and 2. The absolute configurations of their
aglycones were determined by comparing the experimental and
calculated ECD spectra, and those of the glucopyranosyl were
determined by analysis their derivatives using HPLC method.
(
4
.3. Extraction and isolation
Dried twigs of C. oliveri were powdered and percolated with 95%
ethanol. The ethanol extract was dissolved in 2% hydrochloric acid
and then extracted with CHCl . The acidic layer was basified to pH
0 with aqueous ammonia and then extracted with CHCl . The
solution was concentrated to give a residue (20 g), which
3
4
4
. Experimental
1
CHCl
3
3
.1. General
was separated by
a
silica gel column using CHCl
3
-MeOH
(
1:0 ? 1:1) as eluent, affording 5 fractions (Fr1-5). Fr-4 (4.8 g)
HR-ESIMS measurements were carried out on Thermo LTQ Orbi-
trap XL mass spectrometer (Thermo Electron, Bremen, Germany).
IR spectra were recorded on a PerkinElmer Spectrum 100 FT-IR
was subjected to silica gel column using CDCl
(
3
-MeOH
30:1 ? 5:1) as a gradient eluent to afford 6 sub-fractions 1–6.
Table 1
1
H (600 MHz, d in ppm, J in Hz) and 13C NMR (150 MHz, d in ppm) data of compounds 1–4 in CD
3
OD
1
2
3
4
d
C
d
H
d
C
d
H
d
C
d
H
d
C
d
H
1
2
3
4
5
130.0
132.0
48.5
142.4
115.1
6.49 (d, 11.4)
129.2
133.6
48.4
142.6
114.9
6.52 (d, 11.4)
131.2
130.0
53.1
142.2
115.2
6.30 (d, 15.9)
130.5
132.0
53.1
142.3
115.1
6.33 (d, 15.9)
5.65 (dd, 11.4, 9.7)
4.50 (dd, 9.7, 6.1)
6.01 (ddd, 16.7, 10.8, 6.1)
5.12 (br d, 16.7)
5.71 (dd, 11.4, 10.0)
4.44 (dd, 10.0, 6.2)
6.00 (ddd, 15.9, 10.7, 6.2)
5.11 (br d, 15.9)
6.19 (dd, 15.9, 6.8)
4.13 (dd, 6.8, 6.8)
6.08 (ddd, 17.1, 10.1, 6.8)
5.12 (br d, 10.1)
6.28 (dd, 15.9, 6.7)
4.10 (dd, 6.7, 6.7)
6.08 (ddd, 17.2, 10.2, 6.7)
5.11 (br d, 10.2)
5
.12 (br d, 10.8)
5.10 (br d, 10.7)
5.07 (br d, 17.1)
5.06 (br d, 17.2)
0
0
0
0
0
0
0
0
1
2
3
4
1
2
3
4
129.8
130.9
116.0
157.7a
138.8
129.6
117.8
157.6a
102.3
74.9
132.7
130.8
117.4
158.1
135.4
129.6
116.3
157.0
102.1
74.9
130.4
128.4
116.3
158.0b
138.3
130.0
117.7
157.7b
102.3
74.9
133.3
128.2
117.7
158.4
135.0
130.0
116.2
157.0
102.2
74.9
0
0
, 6
, 5
7.11 (d, 8.5)
6.73 (d, 8.5)
7.23 (d, 8.7)
7.06 (d, 8.7)
7.20 (d, 8.6)
6.70 (d, 8.6)
7.30 (d, 8.7)
7.02 (d, 8.7)
0
0
0
0
00
00
, 6
, 5
7.14 (d, 8.7)
7.04 (d, 8.7)
7.02 (d, 8.5)
6.72 (d, 8.5)
7.17 (d, 8.7)
7.06 (d, 8.7)
7.06 (d, 8.5)
6.74 (d, 8.5)
Glu-1
Glu-2
Glu-3
Glu-4
Glu-5
Glu-6
4.88 (d, 7.4)
3.45 (m)
3.44 (m)
3.38 (m)
3.42 (m)
4.92 (d, 7.4)
3.46 (m)
3.45 (m)
3.39 (m)
3.44 (m)
4.89 (d, 7.4)
3.45 (m)
3.44 (m)
3.39 (m)
3.42 (m)
4.88 (d, 7.4)
3.45 (m)
3.44 (m)
3.39 (m)
3.42 (m)
78.0
71.3
78.1
62.5
78.0
71.3
78.1
62.5
77.9
71.3
78.1
62.5
77.9
71.3
78.1
62.4
3.88 (dd, 12.1, 2.1)
3
3.90 (dd, 12.1, 2.1)
3.69 (dd, 12.1, 5.6)
3.89 (dd, 12.1, 2.1)
3.69 (dd, 12.1, 5.5)
3.89 (dd, 12.1, 2.1)
3.69 (dd, 12.1, 5.5)
.69 (dd, 12.1, 5.5)
a,b
Interchangeable.

F.-C. Meng et al. / Tetrahedron: Asymmetry 28 (2017) 1686–1689
1689
Sub-fraction 4 (1.1 g) was subjected to silica gel column chro-
matography with the solvent system CHCl -MeOH (15:1 ? 10:1)
added and heated for 1 h.13 Finally, the solutions were passed
through a 0.45 m syringe filter for HPLC analysis (Agilent 1200,
3
l
to give 4 sub-fractions. Further chiral separation of sub-fraction 3
250 mm ꢁ 4.6 mm i.d. Cosmosil 5C18-AR-II, acetonitrile: 0.5%
aqueous trifluoroacetic acid solution 25:75, 0.8 mL/min, 250 nm).
The standard solutions of glucose (5 mg) were treated as described
was performed on an Agilent 1200 HPLC equipped with a 250
Ò
mm ꢁ 4.6 mm Lux
Cellulose-3
5
l
m
3 2
column (CH CN:H O
2
5:75). Finally, compound 1 (1.0 mg), 2 (2.0 mg), 3 (2.9 mg) and
(4.0 mg) were obtained.
above. The peaks of glucose derivative were observed at t
-glucose 20.23, 2 -glucose 20.21, 3 -glucose 20.18, 4
0.16 (reference -glucose 18.38, -glucose 20.14).
R
(min): 1
-glucose
4
D
D
D
D
2
L
D
0
0
4
.3.1. (3S)-4 -O-b-
Amorphous powder, C23
KBr) max: 3133, 2926, 2855, 1660, 1611, 1510, 1401, 1234, 1074
D-Glucopyranosylnyasol 1
20
H
26
O
7
, [
a]
D
= +119.0 (c 0.03, MeOH), IR
Acknowledgments
(
m
ꢀ1
cm ; UV (MeOH) kmax (log
ESIMS m/z 432.2003 [M+NH
e
): 207 (4.02), 257 (3.76) nm; HR-
This study was supported by grants from the Research Commit-
tee of the University of Macau [MYRG2016-00046-ICMS-QRCM],
Macao; Guangzhou Science and Technology Innovation funding,
PR China; and Macao Science and Technology Development Fund
[042-2014-A1], Macao.
+
4
]
(calcd for C23
H
30
O
7
N, 432.2022)
, 413.1600); CD
OD, 600 MHz)
ꢀ
and m/z 413.1585 [MꢀH] (calcd for C23
25 7
H O
(
MeOH): [h]228 ꢀ8800, [h]255 +62400; 1H NMR (CD
3
1
3
3
and C NMR (CD OD, 150 MHz) data see Table 1.
0
4
.3.2. (3S)-4 -O-b-
D
-Hlucopyranosylnyasol 2
A. Supplementary data
20
Amorphous powder, C23
KBr) max: 3274, 2931, 2859, 1664, 1614, 1405, 1231 1077 cm
UV (MeOH) kmax (log ): 206 (3.93), 252 (3.72) nm; HR-ESIMS
26 7 D
H O , [a] = +95.0 (c 0.1, MeOH), IR
ꢀ
1
(
m
;
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.tetasy.2017.10.017.
e
+
m/z 432.2000 [M+NH
4
]
(calcd for C23H
30
O
7
N, 432.2022) and m/z
ꢀ
4
[
13.1586 [MꢀH] (calcd for C23
H O , 413.1600); CD (MeOH):
25 7
References
1
h]228 ꢀ18500, [h]254 +55900, [h]290 ꢀ2100; H NMR (CD
3
OD, 600
1
3
MHz) and C NMR (CD OD, 150 MHz) data see Table 1.
3
1. Editorial Committee of the Administration Bureau of Chinese Plant Medicine.
Flora of China; Science Press: Beijing, 1978; Vol 7, p 434.
2
3
.
.
Abdelkafi, H.; Nay, B. Nat. Prod. Rep. 2012, 29, 845–869.
Ma, Z. W.; He, G. F.; Yin, W. F. J. Integr. Plant Biol. 1986, 6, 13.
0
0
4
.3.3. (3S)-4 -O-b-
Amorphous powder, C23
KBr) max: 3168, 2928, 2858, 1654, 1624, 1414, 1247, 1085
cm ; UV (MeOH) kmax (log ): 206 (4.30) nm; HR-ESIMS m/z
(calcd for N, 432.2022), m/z
, 459.1655) and m/z
, 413.1600); CD (MeOH):
D-Glucopyranosylhinokiresinol 3
20
H
26
O
7
, [
a]
D
ꢀ16.6 (c 0.05, MeOH), IR
4. Zhang, F. X.; Wang, Z. H.; Pan, W. D.; Li, Y. J.; Mai, L. T.; Sun, J. Q. J. Integr. Plant
Biol. 1978, 2, 5.
5
(
m
.
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in Natural Products Chemistry; Rahman, A., Ed.; Elsevier B. V.: Amsterdam, 2017;
pp 339–373. Chapter 10.
ꢀ1
e
+
4
4
4
[
(
32.2001 [M+NH
59.1639 [M+HCOO] (calcd for C24
4
]
C
23
H
30
O
7
-
6. Badgujar, V.B.; Ansari, M.T.; Abdullah, M.S.; Badgujar, S.V. World J. Pharm.
Pharm. Sci. 2015, 4, 1380–1391.
7
8. Moirangthem, D. S.; Laishram, S.; Rana, V. S.; Borah, J. C.; Talukdar, N. C. Nat.
Prod. Res. 2015, 29, 1161–1165.
H
27
O
9
ꢀ
13.1585 [MꢀH] (calcd for C23
25 7
H O
. Chung, C. Am. J. Health-Syst. Ph. 2014, 71, 279.
1
h]229 +5300, [h]242 +3200, [h]261 +2000, [h]284 ꢀ5400; H NMR
13
CD OD, 600 MHz) and C NMR (CD OD, 150 MHz) data see
3
3
9. Zeng, L. B.; Vrijmoed, L. L. P. J. Serb. Chem. Soc. 2012, 77, 437–451.
Table 1.
10. He, Y. R.; Shen, Y. H.; Shan, L.; Yang, X.; Wen, B.; Ye, J.; Yuan, X.; Li, H. L.; Xu, X.
K.; Zhang, W. D. RSC Advances. 2015, 5, 4126–4134.
11. Ma, S. J.; Shi, X. L.; Yan, H.; Ma, Z. Q.; Zhang, X. Ind. Crop. Prod. 2016, 94, 658–
0
4
.3.4. (3S)-4 -O-b-
Amorphous powder, C23
KBr) max: 3138, 2935, 2848, 1651, 1616, 1406, 1242, 1081
D-glucopyranosylhinokiresinol 4
20
664.
H
26
O
7
, [a
]
D
ꢀ38.3 (c 0.13, MeOH), IR
1
2. Meng, F. C.; Yuan, C.; Huang, X. J.; Wang, W. J.; Lin, L. G.; Zhang, X. T.; Jiao, H. Y.;
(
m
Zhang, Q. W. Phytochem. Lett. 2016, 15. 118-112.
13. Messana, I.; Msonthi, J. D.; De Vicente, Y.; Multari, G.; Galeffi, C. Phytochemistry.
1989, 28, 2807–2809.
4. Gao, F.; Carr, J. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2014, 136, 2149–2161.
5. Akiyama, K.; Gao, F.; Hoveyda, A. H. Angew. Chem. Int. Ed. 2010, 49, 419–423.
16. Hamilton, J. Y.; Sarlah, D.; Carreira, E. M. J. Am. Chem. Soc. 2013, 135, 994–997.
17. Minami, E.; Taki, M.; Takaishi, S.; Iijima, Y.; Tsutsumi, S.; Akiyama, T. Chem.
Pharm. Bull. 2000, 48, 389–392.
ꢀ1
cm ; UV (MeOH) kmax (log
ESIMS m/z 432.2002 [M+NH
e
): 208 (4.04), 261 (4.01) nm; HR-
+
4
]
(calcd for C23
30
H O
7
N, 432.2022)
1
1
ꢀ
and m/z 413.1587 [MꢀH] (calcd for C23
H O , 413.1600); CD
25 7
1
(
6
MeOH): [h]227 +6400, [h]240 +4600, [h]284 ꢀ4700; H NMR (CD
3
OD,
1
3
3
00 MHz) and C NMR(CD OD, 150 MHz) data see Table 1.
1
1
2
2
8. Lassen, P. R.; Skytte, D. M.; Nielsen, Hemmingsen L. S. F.; Freedman, T. B.; Nafie,
L. A.; Christensen, S. B. J. Nat. Prod. 2005, 68, 1603–1609.
9. Muraoka, O.; Zheng, B. Z.; Fujiwara, N.; Tanabe, G. J. Chem. Soc. Perkin Trans.
4
.4. Acid hydrolysis
1996, 1, 405–411.
Compounds 1–4 (each 0.5–2 mg) were hydrolyzed in 2 mL of 2
0. Hirose, T.; Oishi, N.; Nagaki, H.; Nakatsuka, T. Tetrahedron Lett. 1965, 41, 3665–
3668.
1. Enzell, Curt R.; Thomas, Brian Russell; Wahlberg, I. Tetrahedron Lett. 1967, 23,
mol/L HCl at 80 °C water-bath for 2 h. After remove the solvent, the
residues were dissolved in 0.5 mL pyridine containing 5 mg of
2211–2217.
L-cysteine methyl ester. The mixtures were then kept at 60 °C
water-bath for 1 h, after which O-tolyl isothiocyanate (5 mg) was