2015

NPC Natural Product Communications Vol. 10

No. 12
Lycopodium Alkaloids from Diphasiastrum complanatum 2091 - 2094
Yu Tang, Juan Xiong and Jin-Feng Hu*

Department of Natural Products Chemistry, School of Pharmacy, Fudan University, No. 826 Zhangheng Road,
Shanghai 201203, PR China

jfhu@fudan.edu.cn

Received: August 20th, 2015; Accepted: October 2nd, 2015

One new lycopodine-type Lycopodium alkaloid, dehydroisofawcettiine N-oxide (1) and eleven known analogues (2−12) were isolated from the whole plant of
Diphasiastrum complanatum. The new structure was established on the basis of spectroscopic methods, including 2D NMR techniques. The absolute
configurations of 2 and its new N-oxide derivative (1) were deduced by chemical transformation combined with Cotton effects in their electronic circular
dichroism (ECD) spectra.

Keywords: Lycopodium alkaloids, Diphasiastrum complanatum, Absolute configuration, Chemical transformation, ECD.

Diphasiastrum complanatum (L.) Holub (syn.: Lycopodium

complanatum L.) belonging to the family Lycopodiaceae and
commonly known as “Guo-Jiang-Long” in Chinese, is a club moss
mainly distributed in temperate and subtropical areas. This plant has
been used as a folk medicine for the treatment of arthritic pain,
quadriplegia, contusion, and blood stasis [1]. Previous
investigations of this plant led to the isolation of a number of
Lycopodium alkaloids [2] with interesting bioactivities, such as
enhancement of mRNA expression for nerve growth factor (NGF)
[2d,2i], cytotoxicity against murine leukemia L1210 cells [2i], and
antimicrobial activity [2i]. During the continuing program of
discovery of novel bioactive alkaloids from club mosses [3], the
chemical constituents of D. complanatum were reinvestigated.
Herein described are the isolation and structural determination of
one new (1) and eleven known (2–12) Lycopodium alkaloids
(Figure 1) from the title plant.

The air-dried and pulverized whole plant of D. complanatum was

extracted with 90% MeOH at room temperature and then worked up
as usual [3,4] to give the crude alkaloid-containing extract. From
this, 12 Lycopodium alkaloids were isolated and characterized
(1–12, Figure 1). Comparing their spectroscopic data and
physicochemical properties observed and reported, the known
alkaloids were identified as dehydroisofawcettiine (2) [5],
lycopodine (3) [6], lycopodine N-oxide (4) [7], L.20 (= 6α-
hydroxylycopodine, 5) [8], clavolonine (6) [9,10], flabelliformine
(7) [10], 6-epi-8β-acetoxylycoclavine (8) [11], acetylfawcettiine (9)
[6], lycoclavine (10) [12], 12-deoxyhuperzine O (11) [13], and
lycodine (12) [14]. Among them, alkaloids 2, 4, 6, 8 and 9 are
reported here for the first time from the title plant.
Compound 1 showed an [M+H]+ ion peak at m/z 322.2016 (calcd
322.2013) in its positive mode HRESIMS, corresponding to the
molecular formula C18H27NO4. The IR absorption bands at 1707
and 1733 cm-1 implied the presence of ester and ketone carbonyl
groups. The 1H and 13C NMR data of 1 (Table 1), with the aid of an
HSQC NMR experiment, showed the presence of one methyl
doublet at δH 0.94 (3H, d, J = 6.2 Hz, Me-16; δC 19.0), eight sp3
methylenes, five sp3 methines (including one oxymethine at δH 4.62
(1H, dd, J = 11.0, 4.1 Hz, H-8), δC 79.2), one sp3 (δ 74.4)
quaternary carbon, and one carbonyl group (δC 207.9) for the
skeleton, along with signals assignable to an acetyl group [δH 2.06
Figure 1: Chemical structures of compounds 1–12.
(3H, s); δC 21.3 and 170.4]. The above spectroscopic data showed
high similarity to those of a known lycopodine-type alkaloid,
dehydroisofawcettiine (2) [5]; however, the complete 1H and 13C
NMR data of 2 have never been reported until the present study.
Differing from 2, the molecular formula of 1 contains one more
oxygen atom. Meanwhile, the 13C NMR shifts of C-1 (δC 64.4), C-9
(δC 59.8) and C-13 (δC 74.2) neighboring the N-atom in 1 were all
shifted to lower field compared with the corresponding carbons
[δC 47.0 (C-1), 46.9 (C-9) and 59.3 (C-13)] of compound 2 (see
Experimental section). Thus, compound 1 was assumed to be the N-
oxide derivative of 2, which was confirmed by further detailed 2D
NMR (COSY and HMBC) spectroscopic analyses of 1 (Figure 2).
The relative configuration of 1 was then found to be the same as
that of dehydroisofawcettiine (2) from the magnitudes of JH-8, H-15
(11.2 Hz) and JH-14a, H-15 (13.0 Hz), and diagnostic NOE correlations
of H-8/H-12 (δ 2.85, br d, J = 13.8 Hz), H-12/Ha-14 (δ 2.63, dd, J =
14.4, 14.4 Hz), H-15 (δ 1.56, m)/Ha-6 (δ 2.57, br d, J = 16.4 Hz),
and Hb-6 (δ 2.35, dd, J = 16.4, 6.3 Hz)/H-4 (δ 3.01, dd, J = 12.2, 3.7
Hz) (Figure 2).
2092 Natural Product Communications Vol. 10 (12) 2015 Tang et al.

Table 1: 1H (400 MHz) and 13C (100 MHz) NMR data a, b for alkaloid 1.
No. δH, mult (J in Hz) δC
1a 3.60, ddd (13.5, 13.5, 4.4) 64.4 CH2
1b 3.19, br d (13.5)
2a 1.92, m 21.3 CH2
2b 1.85, m,
3a 2.22, br d (14.6) 17.5 CH2
3b 1.70, m, m
4 3.01, dd (12.2, 3.7) 48.8 CH
5 207.9 C
6a 2.57, br d (16.4) 36.2 CH2
6b 2.35, dd (16.4, 6.3)
7 2.44, m 39.1 CH
8 4.62, dd (11.0, 4.1) 79.1 CH
9a 3.96, ddd (12.6, 12.6, 3.0) 59.8 CH2
9b 3.08, br d (12.6)
10a 2.78, m 20.1 CH2
10b 1.78, m
11a 1.91, m 23.3 CH2
11b 1.68, m, Figure 3: ECD spectra of compounds 1–3.
12 2.85, br d (13.8) 36.4 CH
13 74.2 C
14a 2.63, dd (14.4, 14.4) 33.1 CH2
14b 2.10, dd (14.4, 5.0) OAc OAc
15 1.56, m 30.4 CH
16 0.94, d (6.2) 19.0 CH3
8-OAc 2.06, s 21.3 CH3 O O
170.4 C m-CPBA
a
Assignments were made by a combination of 1D and 2D NMR experiments;
b
Recorded in CDCl3. CH 2Cl2, 0°C, 3h
O
N N
CH3 OCO OAc
H H
O Ha O
Ha
COSY: 2 1
H Hb Scheme 1: Chemical transformation from 2 to 1.
HMBC: H C
O O H
N N
NOE: H H Experimental
General experimental procedures: Optical rotations were measured
1 on an Autopol IV automatic polarimeter, IR spectra on an Avatar
Figure 2: COSY, key HMBC and NOE correlations of compound 1. 360 ESP FTIR spectrometer, ECD spectra on a JASCO-810
As previously described by Ayer and Altenkirk [15], the spectropolarimeter, and NMR spectra on a Bruker Avance III 400
lycopodine-like alkaloids with a carbonyl group at C-5 and in which MHz spectrometer. Chemical shifts are expressed in δ (ppm), and
the nitrogen lone pair is equatorial to ring A consistently display referenced to the residual solvent signals. ESIMS were measured on
two Cotton effects above 200 nm, a positive around 288 nm due to an Agilent 1100 series mass spectrometer, and HRESIMS on an AB
n→π transition and a negative centered at 223 nm associated with SCIEX Triple TOF 5600+ spectrometer. Semi-preparative HPLC
σ-coupled p interaction. In good agreement with this assumption, was performed on a Waters e2695 system coupled with a Waters
the electronic circular dichroism (ECD) spectrum of 2998 Photodiode Array Detector and an ODS column (5 μm, 250 ×
dehydroisofawcettiine (2) exhibited a positive Cotton effect at 295 10 mm, SunFire). Column chromatography (CC) was performed
nm (Δε +1.09) and a negative one at 214 nm (Δε –1.85), which using silica gel (200-300 mesh, Kang-Bi-Nuo Silysia Chemical
matched well with that of lycopodine (3) [15], as depicted in Figure Ltd., Yantai, China), and Sephadex LH-20 (GE Healthcare Bio-
3. Thus, the absolute configuration of 2 could be unequivocally Sciences AB, Uppsala, Sweden). Silica gel-precoated plates
determined as 4S,7S,8R,12R,13R,15S. In the case of alkaloid 1, due (GF254, 0.25 mm, Kang-Bi-Nuo Silysia Chemical Ltd., Yantai,
to the disappearance of the nitrogen lone pair after oxidation, it is China) were used for TLC. Compounds were visualized using UV
hard to judge the related Cotton effects since its ECD curve almost light (254 and/or 365 nm) and by spraying with Dragendorff’s
flattened (Figure 3). Nevertheless, the absolute configuration of 1 reagent.
was established to be the same as that of 2 by chemical
transformation. In a supplementary oxidation experiment, Plant materials: The whole plant of D. complanatum was collected
compound 2 was treated with one equivalent of m-CPBA to produce in October 2013 from Bijie in Guizhou Province of China. A
its N-oxide derivative (Scheme 1), which was identical to 1 by voucher specimen (No. 20131007) was deposited at the Herbarium
means of HPLC, optical rotation, and spectroscopic analyses. of the Department of Natural Products Chemistry, School of
Accordingly, the structure of 1 was defined as Pharmacy at Fudan University. The plant was identified by Prof.
(4S,7S,8R,12R,13R,15S)-dehydroisofawcettiine N-oxide. Indeed, Qiang Luo (Guizhou University of Engineering Science, Bijie,
naturally occurring N-oxide derivatives of Lycopodium alkaloids Guizhou Province of China).
have often been encountered [2h,7,16].
Extraction and isolation: The air-dried and pulverized whole plant
Similar to casuarinines A–J, lycodine-type alkaloids from of D. complanatum (1.6 kg) was extracted with 90% MeOH (5 × 8
Lycopodiastrum casuarinoides [3], all the isolates were evaluated L) at room temperature, and the MeOH extract (170 g) was
for their neuroprotective and anti-acetylcholinesterase (AChE) partitioned between EtOAc and 3% tartaric acid. The water-soluble
effects, but none of them were active. They also did not show any portion, adjusted to pH 9 with sat. Na2CO3, was partitioned with
significant cytotoxicity against human A-549 and NCI-H460 cancer CHCl3. The CHCl3-soluble portion (3.9 g) was loaded on a silica
cell lines. gel column, eluted with a gradient of CH2Cl2/MeOH (1:0–0:1) to
Alkaloids from Diphasiastrum complanatum Natural Product Communications Vol. 10 (12) 2015 2093

afford fractions 1–8. Fraction 2 (40 mg) was chromatographed on
Sephadex LH-20 (CH2Cl2/MeOH, 2:1) to afford 2 (1.9 mg) and 11
(6.1 mg). Fraction 3 (90 mg) was subjected to silica gel CC
(CH2Cl2/MeOH, 50:1) and then purified by semi-preparative HPLC
[MeOH-H2O (containing 0.05% Et2NH, v/v) 60:40, v/v; flow rate,
3.0 mL/min] to furnish 1 (1.7 mg, tR = 10.4 min) and 4 (5.6 mg, tR =
12.0 min). Compounds 3 (16.0 mg, tR = 13.1 min) and 12 (2.7 mg,
tR = 10.7 min) were isolated from fraction 4 (80 mg) by semi-
preparative HPLC [MeOH-H2O (containing 0.05% Et2NH, v/v)
50:50, v/v; flow rate, 3.0 mL/min]. Fraction 5 (200 mg) was
subjected to gel permeation chromatography (GPC) on Sephadex
LH-20 (CH2Cl2/MeOH, 2:1) to afford 9 (29.5 mg). Compound 5
(7.2 mg, tR = 14.4 min) was obtained from fraction 6 (210 mg) by
semi-preparative HPLC [MeCN-H2O (containing 0.05% Et2NH,
v/v) 30:70, v/v; flow rate, 3.0 mL/min]. Fraction 7 (50 mg) was
chromatographed on Sephadex LH-20 (MeOH) to furnish 6 (9.4
mg,). Fraction 8 (300 mg) was separated by Sephadex LH-20
(MeOH) and further purified by semi-preparative HPLC [MeCN-
H2O (containing 0.05% Et2NH, v/v) 45:55, v/v; flow rate, 3.0
mL/min] to afford 7 (6.1 mg, tR = 16.0 min), 8 (2.1 mg, tR = 10.8
min), and 10 (1.7 mg, tR = 20.4 min).
Dehydroisofawcettiine N-oxide (1)
[α]D25: +30.0 (c 0.1, MeOH).
IR (film): 3417, 2923, 1733, 1707, 1627, 1377, 1244, 1048 cm-1.
1
H and 13C NMR: Table 1.
HRESIMS: m/z [M+H]+ calcd for C18H27NO4: 322.2013; found:
322.2016.
of the N-oxide product of 2. All the spectroscopic data (1H NMR,
ESIMS and [α]D25) were identical with those of natural 1.
Dehydroisofawcettiine (2)
[α]D25: +34.0 (c 0.1, MeOH).
ECD (c 6.56 × 10-4 M, MeOH) λmax (Δε): 214 (–1.85), 295 (+1.09)
nm.
1
H NMR (400 MHz, CDCl3): δ 4.59 (1H, dd, J = 11.0, 4.2 Hz, H-8),
3.31 (1H, ddd, J = 14.2, 14.2, 3.7 Hz, H-1a), 3.14 (1H, ddd, J =
12.4, 12.4, 2.7 Hz, H-9a), 2.93 (1H, dd, J = 11.8, 3.1 Hz, H-4), 2.67
(1H, dd, J = 13.9, 4.9 Hz, H-14a), 2.63 (1H, br d, J = 12.4 Hz, H-
9b), 2.55 (1H, dd, J = 14.2, 4.9 Hz, H-1b), 2.49 (1H, dd, J = 17.9,
3.6 Hz, H-6a), 2.33 (1H, d, J = 17.9 Hz, H-6b), 2.32 (1H, m, H-3a),
2.10 (1H, m, H-7), 2.07 (3H, s, CH3CO), 1.88 (1H, m, H-2a), 1.84
(1H, m, H-10a), 1.77 (1H, m, H-12), 1.72 (1H, m, H-10b), 1.65
(1H, m, H-11a), 1.63 (1H, m, H-13b), 1.58 (1H, m, H-11b), 1.53
(1H, m, H-15), 1.39 (1H, br d, J = 13.8 Hz, H-2b), 1.09 (1H, dd, J =
13.9, 13.9 Hz, H-14b), 0.89 (3H, d, J = 6.2 Hz, Me-16);
13
C NMR (100 MHz, CDCl3): δ 212.6 (C-5, C), 170.8 (CH3CO, C),
80.4 (C-8, CH), 59.3 (C-13, C), 47.0 (C-9, CH2), 46.9 (C-1, CH2),
43.3 (C-12, CH), 42.9 (C-4, CH), 41.6 (C-14, CH2), 39.6 (C-7, CH),
37.0 (C-6, CH2), 30.1 (C-15, CH), 25.9 (C-10, CH2), 24.7 (C-11,
CH2), 21.1 (CH3CO, CH3), 19.2 (C-3, CH2), 18.9 (C-16, CH3), 18.5
(C-2, CH2)
ESIMS: m/z 306 [M+H]+.
Supplementary data: NMR spectra of compounds 1 and 2 are
available in electronic form on the publisher’s website.

m-CPBA oxidation of dehydroisofawcettiine (2): Similar to the
reported literature [7], compound 2 (4.0 mg, 0.01312 mmol) was
dissolved in CH2Cl2 (2 mL) to which m-CPBA (2.9 mg, 0.0142
mmol) was added. The reaction mixture was left at 0°C for 3 h and
then evaporated to give a residue, which was applied to semi-
preparative HPLC [MeOH-H2O (containing 0.05% diethylamine,
v/v) 60:40, v/v; flow rate, 3.0 mL/min], giving 3.4 mg (yield 80%)
Acknowledgments - The authors gratefully acknowledge Prof.
Qiang Luo (Guizhou University of Engineering Science, PR China)
for the plant collection and identification. This work was supported
by NSFC grants (Nos. 21472021, 81273401, 81202420), grants
from the Ph.D. Programs Foundation of Ministry of Education
(MOE) of China (Nos. 20120071110049, 20120071120049), and
the National Basic Research Program of China (973 Program, Grant
No. 2013CB530700).

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