New terpenoid glycosides obtained from Rosmarinus officinalis L. aerial parts

Article abstract of DOI:10.1016/j.fitote.2014.09.004

Five new terpenoid glycosides, named as officinoterpenosides A₁ (1), A₂ (2), B (3), C (4), and D (5), together with 11 known ones, (1S,4S,5S)-5-exo-hydrocamphor 5-O-β-d-glucopyranoside (6), isorosmanol (7), rosmanol (8), 7-methoxyrosmanol (9), epirosmanol (10), ursolic acid (11), micromeric acid (12), oleanolic acid (13), niga-ichigoside F₁ (14), glucosyl tormentate (15), and asteryunnanoside B (16), were obtained from the aerial parts of Rosmarinus officinalis L. Their structures were elucidated by chemical and spectroscopic methods (UV, IR, HRESI-TOF-MS, 1D and 2D NMR). Among the new ones, 1 and 2, 3 and 4 are diterpenoid and triterpenoid glycosides, respectively; and 5 is a normonoterpenoid. For the known ones, 6 was isolated from the Rosmarinus genus first, and 15, 16 were obtained from this species for the first time.

Full text of DOI:10.1016/j.fitote.2014.09.004

Fitoterapia 99 (2014) 78–85
Contents lists available at ScienceDirect
Fitoterapia
journal homepage: www.elsevier.com/locate/fitote
New terpenoid glycosides obtained from Rosmarinus officinalis L.
aerial parts
Yi Zhang , Tiwalade Adegoke Adelakun b,c, Lu Qub,c, Xiaoxia Li b,c, Jian Li b,c
a
,
a,b,c
a,b,c,
Lifeng Han
, Tao Wang
⁎
a
Tianjin State Key Laboratory of Modern Chinese Medicine, 312 Anshanxi Road, Nankai District, Tianjin 300193, China
Tianjin Key Laboratory of TCM Chemistry and Analysis, Tianjin University of Traditional Chinese Medicine, 312 Anshan Road, Nankai District, Tianjin 300193, China
Institute of Traditional Chinese Medicine, Tianjin University of Traditional Chinese Medicine, 312 Anshan Road, Nankai District, Tianjin 300193, China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
1 2
Five new terpenoid glycosides, named as officinoterpenosides A (1), A (2), B (3), C (4), and D
Received 26 July 2014
Accepted in revised form 23 August 2014
Available online 6 September 2014
(5), together with 11 known ones, (1S,4S,5S)-5-exo-hydrocamphor 5-O-β-D-glucopyranoside (6),
isorosmanol (7), rosmanol (8), 7-methoxyrosmanol (9), epirosmanol (10), ursolic acid (11),
micromeric acid (12), oleanolic acid (13), niga-ichigoside F (14), glucosyl tormentate (15), and
1
asteryunnanoside B (16), were obtained from the aerial parts of Rosmarinus officinalis L. Their
structures were elucidated by chemical and spectroscopic methods (UV, IR, HRESI-TOF-MS, 1D
and 2D NMR). Among the new ones, 1 and 2, 3 and 4 are diterpenoid and triterpenoid glycosides,
respectively; and 5 is a normonoterpenoid. For the known ones, 6 was isolated from the
Rosmarinus genus first, and 15, 16 were obtained from this species for the first time.
Keywords:
Rosmarinus officinalis
Terpenoid glycosides
Normonoterpenoid
Diterpenoid
©
2014 Elsevier B.V. All rights reserved.
Triterpenoid
1
. Introduction
The two types of compounds that are mainly responsible for
the biological activities of this plant are the volatile fraction and
the phenolic constituents. The derived essential oils are mainly
used in local application for their balsamic, antispasmodic and
anti-inflammatory activities [12]. The phenolic constituents
are mainly constituted by three groups: phenolic diterpenes
of an abietic acid related structures (carnosol, carnosic acid,
rosmadial or rosmanol, etc.), and flavonoids (genkwanin,
cirsimaritin) derived from two common flavones: apigenin
and luteolin, and phenolic acids (rosmarinic acid) [13]. Some
scientists have observed that among these constituents, carnosic
acid, carnosol, and abietane diterpenes are the main antioxidant
compounds present in Rosemary [14]. Are there any other active
terpenoids in the plant? And then, the phytochemical research
for it was developed. As a result, 16 terpenoids including five
Rosmarinus officinalis L. (Lamiaceae), popularly known
as Rosemary in English and 迷迭香 in Chinese, is a shrub
widely distributed in Europe, Asia, and Africa. And one of its
elective growing areas is the Mediterranean basin where
spontaneous plants are diffusely distributed. Rosemary has
been traditionally used as a culinary spice, mainly to modify
or to improve food flavors as well as in folk medicine, being a
greatly valued medicinal herb [1]. Nowadays, it is one of
the most appreciated sources of natural bioactive compounds
which are of special interest in functional food industries. In
fact, this plant exerts various pharmacological activities, such as
hepatoprotective [2], antibacterial [3], antithrombotic [4],
antiulcerogenic [5], diuretic [6], antidiabetic [7], antinociceptive
[8], anti-inflammatory [9], antitumor [10], and antioxidant [11]
new ones, officinoterpenosides A
1 2
(1), A (2), B (3), C (4), and
D (5), together with 11 known isolates, (1S,4S,5S)-5-exo-
hydrocamphor 5-O-β-D-glucopyranoside (6) [15], isorosmanol
activities.
(
7) [16], rosmanol (8) [17], 7-methoxyrosmanol (9) [17],
epirosmanol (10) [18], ursolic acid (11) [19], micromeric acid
(12) [20], oleanolic acid (13) [21], niga-ichigoside F (14) [22],
⁎
Corresponding author at: Tianjin Key Laboratory of TCM Chemistry and
Analysis, Tianjin University of Traditional Chinese Medicine, 312 Anshan Road,
Nankai District, Tianjin 300193, China. Tel./fax: +86 22 5959 6163.
1
http://dx.doi.org/10.1016/j.fitote.2014.09.004
0367-326X/© 2014 Elsevier B.V. All rights reserved.

Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
79
glucosyl tormentate (15) [23], and asteryunnanoside B
16) [24] were isolated and identified. Among the new
5-O-β-D-glucopyranoside (6, 3.5 mg). Fraction 8 (5480.0 mg)
2
was subjected to PHPLC through gradient elution [MeOH–H O
(
ones, 1 and 2, 3 and 4 are diterpenoid and triterpenoid
glycosides, respectively; and 5 is a normonoterpenoid. This
paper deals with the isolation and structure elucidation of
the new compounds.
(30:70 → 50:50 → 70:30 → 100:0, v/v)] to yield 22 fractions
(Fr. 8-1–8-22). Fraction 8-9 (121.6 mg) was purified by PHPLC
[CH
(5, 44.0 mg). Fraction 8-21 (70.3 mg) was purified by
PHPLC [CH CN–H O (28:72, v/v)] to yield glucosyl tormentate
(15, 3.8 mg). Fraction 9 (10.0 g) was separated by ODS CC
MeOH–H O (20:80 → 30:70 → 40:60 → 50:50 → 60:40 →
3 2
CN–H O (11:89, v/v)] to yield officinoterpenoside D
3
2
2
. Experimental
[
2
2
.1. General
70:30 → 100:0, v/v)] to yield 14 fractions (Fr. 9-1–9-14).
Fraction 9-10 (1510.0 mg) was purified by Sephadex LH-20 CC
Optical rotations were measured on a Rudolph Autopol® IV
automatic polarimeter. IR spectra were recorded on a Varian
40-IR FT-IR spectrophotometer. UV spectra were obtained on
[CHCl
8). Fraction 9-10-2 (512.2 mg) was subjected to PHPLC
[MeOH–1% CH COOH (45:55, v/v)] to obtain 14 fractions
(Fr. 9-10-2-1–9-10-2-14). Fraction 9-10-2-11 (85.0 mg) was
purified by PHPLC [CH CN–1% CH COOH (23:77, v/v)] to yield
officinoterpenoside C (4, 6.1 mg) and niga-ichigoside F
(14, 34.7 mg). Fraction 10 (6.3 g) was subjected to PHPLC
through gradient elution [MeOH-H O (25:75 → 40:60 →
3
–MeOH (1:1, v/v)] to yield 8 fractions (Fr. 9-10-1–9-10-
6
3
a Varian Cary 50 UV–Vis spectrophotometer. NMR spectra
were determined on a Bruker 500 MHz NMR spectrometer at
3
3
1
13
5
00 MHz for H and 125 MHz for C NMR, with TMS as an
1
internal standard. Positive- and Negative-ion HRESI-TOF-MS
were recorded on an Agilent Technologies 6520 Accurate-Mass
Q-Tof LC/MS spectrometer.
2
60:40 → 80:20 → 100:0, v/v)] to yield 35 fractions (Fr. 10-1–
Column chromatographies (CC) were performed on macro-
porous resin D101 (Haiguang Chemical Co., Ltd., Tianjin, China),
Silica gel (74–149 μm, Qingdao Haiyang Chemical Co., Ltd.,
Qingdao, China), and ODS (50 μm, YMC Co., Ltd., Tokyo, Japan).
Preparative HPLC (PHPLC) column (Cosmosil 5C18-MS-II
10-35). Fraction 10-26 (93.7 mg) was purified by PHPLC
3 3
[CH CN–1% CH COOH (16:84, v/v)] to yield officinoterpenoside
A
2
(2, 7.1 mg). Fraction 10-27 (756.1 mg) was subjected to
Sephadex LH-20 CC (MeOH) to yield 9 fractions (Fr. 10-27-1–
10-27-9). Fraction 10-27-3 (217.5 mg) was purified by
(
20 mm i.d. × 250 mm, Nakalai Tesque, Inc., Tokyo, Japan))
PHPLC [CH
officinoterpenosides A
Fraction 10-31 (198.5 mg) was separated by PHPLC [CH
1% CH COOH (26:74, v/v)] to give 5 fractions (Fr. 10-31-1–10-
3
CN–1% CH
3
COOH (18:82, v/v)] to obtain
(1, 41.2 mg).
CN–
were used to purify the constituents. Pre-coated TLC plates with
Silica gel GF254 (Tianjin Silida Technology Co., Ltd., Tianjin,
China) were used to detect the purity of isolates achieved by
2
(2, 10.7 mg) and A
1
3
3
spraying with 10% aqueous H
.2. Plant material
The dried aerial parts of R. officinalis were collected from
2
SO
4
–EtOH, followed by heating.
31-5). Fraction 10-31-2 (14.1 mg) was purified by Sephadex
LH-20 (MeOH), and officinoterpenoside B (3, 8.2 mg) was
obtained. Asteryunnanoside B (16, 6.3 mg) was isolated from
2
3 3
fraction 10-33 (132.4 mg) by PHPLC [CH CN–1% CH COOH
(28:72, v/v)].
Butarie, Rwanda and identified by Dr. Li Tianxiang (The Hall of
TCM Specimens, Tianjin University of TCM, China). The voucher
specimen was deposited at the Academy of Traditional Chinese
Medicine of Tianjin University of TCM (No. 20110910).
The CHCl
subjected to silica gel CC [CHCl
100:3 → 100:5 → 100:7, v/v) → CHCl
3
partition (200 g) of the rosemary extract was
→ CHCl –MeOH (100:1 →
–MeOH–H O (10:3:1 →
3
3
3
2
2
.3. Extraction and isolation
Table 1
1
H and 13C NMR data for 1 in CD
3
OD.
The dried aerial parts of R. officinalis (2.5 kg) were refluxed
No. δC
δH (J in Hz)
No. δC
δH (J in Hz)
with 95% EtOH. The solvent was evaporated under reduced
pressure to yield the 95% EtOH extract (455 g). Then, the
1
35.8 1.27 (ddd, 3.0, 13.5,
17
22.6 1.18 (d, 6.5)
13.5)
extract (379 g) was partitioned in a CHCl
v/v) to give both CHCl (269 g) and H O (100 g) partitions. Then,
the H O layer (100 g) was subjected to D101 macroporous resin
column chromatography (CC) and eluted with H O and 95%
O (47 g) and 95% EtOH (45 g)
3
–H
2
O mixture (1:1,
3.31 (m, overlapped)
28.4 1.67 (m), 1.76 (m)
78.4 3.18 (dd, 4.5, 11.5)
18
19
20
1′
2′
3′
4′
5′
6′
28.5 1.02 (s)
16.0 0.92 (s)
17.7 1.40 (s)
105.3 4.74 (d, 8.0)
82.9 3.87 (dd, 8.0, 9.0)
77.6 3.75 (dd, 9.0, 9.0)
70.6 3.52 (dd, 9.0, 9.0)
78.3 3.30 (m)
2
3
4
5
6
3
2
2
40.1
–
2
51.3 1.69 (dd, 3.0, 14.0)
36.2 2.58 (dd, 3.0, 17.0)
2.62 (dd, 14.0, 17.0)
EtOH, successively. As a result, H
eluted fractions were obtained.
2
7
8
9
1
200.9
129.6
140.8
41.3
–
–
–
–
–
The EtOH fraction (36 g) was subjected to normal phase
silica gel CC [CHCl → CHCl –MeOH (100:3 → 100:5 → 100:7,
v/v) → CHCl –MeOH–H O (10:3:1 → 7:3:1, v/v/v) → MeOH]
62.0 3.75 (dd, 4.5, 12.0)
3.83 (br. d, ca. 12)
3
3
3
2
0
1″ 105.4 4.86 (d, 8.0)
2″
to yield 11 fractions (Fr. 1–11).
11 148.8
75.6 3.43 (m,
overlapped)
77.5 3.43 (m,
overlapped)
71.1 3.42 (dd, 9.0, 9.0)
78.4 3.34 (m)
2
Fraction 7 (5.5 g) was subjected to ODS CC [MeOH–H O
1
1
2
3
150.2
132.5
–
–
3″
(
20:80 → 30:70 → 40:60 → 50:50 → 60:40 → 70:30 → 100:0,
v/v)] to yield 9 fractions (Fr. 7-1–7-9). Fraction 7-5 (1610.0 mg)
was also purified by PHPLC [CH CN–1% CH COOH (18:82, v/v)],
as a result, 19 fractions (Fr. 7-5-1–7-5-19) were obtained.
Fraction 7-5-6 (36.8 mg) was subjected to PHPLC [CH CN–1%
CH COOH (10:90, v/v)] to offer (1S,4S,5S)-5-exo-hydrocamphor
4″
5″
6″
3
3
14 122.2 7.46 (s)
15 41.0 2.63 (m, overlapped)
.30 (dd, 6.0, 13.0)
68.0 4.16 (m)
62.4 3.68 (dd, 5.0, 12.0)
3.83 (br. d, ca. 12)
3
3
1
6
3

80
Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
Table 2
Table 4
1
H and 13C NMR data for 2 in CD
1
H and 13C NMR data for 4 in CD
3
OD.
3
OD.
No.
1
δ
C
δ
H
(J in Hz)
No.
δ
C
δ
H
(J in Hz)
No.
1
δ
C
δ
H
(J in Hz)
No.
19
δ
C
H
δ (J in Hz)
35.8 1.42 (ddd, 4.0, 14.0, 14.0) 16
68.3 4.12 (m)
22.9 1.11 (d, 6.5)
28.3 1.13 (s)
16.6 1.02 (s)
17.6 1.41 (s)
47.9 0.89 (dd, 12.0, 12.0)
1.94 (dd, 5.0, 12.0)
69.6 3.78 (ddd, 5.0, 9.0, 12.0) 20
41.4 1.10 (dd, 4.0, 13.5)
1.81 (dd, 13.5, 13.5)
36.8 –
28.9 1.09 (m), 1.79 (m)
32.4 1.65 (m), 1.75 (m)
23.8 1.22 (s)
66.2 3.38 (d, 11.5)
4.02 (d, 11.5)
3
.43 (ddd, 4.0, 4.0, 14.0) 17
2
27.7 1.88 (m)
.11 (m)
89.6 3.31 (dd, 4.5, 11.5)
40.4
18
19
20
1′
2′
2
3
4
5
6
7
8
9
2
85.9 3.04 (d, 9.0)
44.4
21
22
23
24
3
4
5
6
–
–
106.7 4.35 (d, 8.5)
75.6 3.22 (dd, 8.5, 9.0)
78.2 3.34 (dd, 9.0, 9.0)
71.6 3.32 (dd, 9.0, 9.0)
77.7 3.26 (m)
57.2 0.97 (dd, 3.0, 11.5)
19.9 1.40 (m), 1.62 (m)
34.2 1.33 (m), 1.47 (m)
51.6 1.79 (dd, 3.0, 14.0)
36.0 2.57 (dd, 3.0, 17.0)
3′
2
–
–
–
–
–
–
–
.62 (dd, 14.0, 17.0)
4′
5′
6′
40.7
49.3 1.63 (dd, 3.0, 9.0)
39.1
24.9 1.92 (m)
–
25
26
27
17.6 0.99 (s)
17.6 0.78 (s)
26.3 1.17 (s)
7
8
9
201.2
129.7
140.9
41.2
149.3
150.6
132.6
62.8 3.67 (dd, 5.0, 12.0)
3.86 (dd, 2.0, 12.0)
10
11
–
28 178.0
–
10
11
12
13
14
15
1″ 107.6 4.56 (d, 8.0)
12 123.6 5.27 (t, 3.5)
13 144.9
14
15
29
30
1′
2′
3′
4′
5′
6′
74.3 3.19 (s)
19.5 0.92 (s)
2″
3″
4″
5″
6″
75.3 3.52 (dd, 8.0, 9.0)
77.9 3.43 (dd, 9.0, 9.0)
70.8 3.47 (dd, 9.0, 9.0)
78.6 3.30 (m)
62.1 3.76 (dd, 4.5, 12.0)
3.83 (dd, 2.0, 12.0)
–
42.9
–
95.8 5.38 (d, 8.0)
73.9 3.33 (dd, 8.0, 9.0)
78.7 3.35 (dd, 9.0, 9.0)
71.1 3.35 (dd, 9.0, 9.0)
78.3 3.41 (m)
29.3 1.17 (m, overlapped)
1.50 (m)
24.0 1.73 (m), 2.05 (m)
121.7 7.44 (s)
40.9 2.68 (dd, 6.5, 13.0)
16
17
3
.19 (dd, 6.5, 13.0)
48.3
–
18
41.8 2.89 (dd, 4.0, 13.5)
62.4 3.65 (dd, 5.0, 11.5)
3.81 (br. d, ca. 12)
7
:3:1, v/v/v) → MeOH] to yield 23 fractions (Fr. 1–23). Fraction
9
(56.3 g) was further subjected to silica gel CC [Pet. Ether
(
PE) → PE–EtOAc (20:1 → 15:1 → 10:1 → 5:1 → 3:1, v/v) →
EtOAc] to yield 19 fractions (Fr. 9-1–9-19). Fraction 9–16
5024.0 mg) was purified by PHPLC [MeOH–H O (90:10, v/v)],
and 13 fractions (Fr. 9-16-1–9-16-13) were given. Fraction
-16-2 (415.5 mg) was subjected to PHPLC [MeOH–H
70:30, v/v)] to obtain 8 fractions (Fr. 9-16-2-1–9-16-2-8),
out of which, isorosmanol (7, 68.3 mg) and rosmanol
8, 128.3 mg) were obtained. Fraction 9-16-2-7 (32.8 mg)
was isolated by PHPLC [CH CN–H O (45:55, v/v)] to yield
subjected to PHPLC [MeOH–H
fractions (Fr. 9-16-4-1–9-16-4-10). Fraction 9-16-4-9
(53.4 mg) was purified by PHPLC [CH CN–H O (41:59, v/
v)] to give 7-methoxyrosmanol (9, 4.7 mg). Fraction 9-16-10
was isolated by PHPLC [MeOH–H O (88:12, v/v)] to yield
2
O (75:25, v/v)] to give 10
(
2
3
2
9
(
2
O
2
micromeric acid (12, 23.7 mg), oleanolic acid (13, 28.3 mg),
and ursolic acid (11, 16.7 mg). Fraction 9-16-12 was purified
(
by PHPLC [MeOH–H
2
O (88:12, v/v)], too, and ten, oleanolic
acid (13, 22.0 mg) was obtained.
3
2
epirosmanol (10, 3.3 mg). Fraction 9-16-4 (629.8 mg) was
2
.3.1. Officinoterpenoside A
1
(1)
Table 3
1
H and 13C NMR data for 3 in C
D N.
5 5
Table 5
No.
1
δ
C
δ
H
(J in Hz)
No.
22
δ
C
δ
H
(J in Hz)
1
H and 13C NMR data for 4 in C
5 5
D N.
48.0 1.23 (m, overlapped)
37.5 1.88 (ddd, 4.5, 13.0,
No.
1
δ
C
δ
H
(J in Hz)
No.
19
δ
C
δ
H
(J in Hz)
1
3.0)
1.98 (m, overlapped)
29.4 1.17 (s)
2
.20 (dd, 4.0, 12.5)
47.7 1.28 (m, overlapped)
41.0 1.44 (m,
2
3
4
5
6
7
8
9
68.6 4.03 (m)
83.9 3.32 (d, 9.5)
23
24
25
26
27
overlapped)
2.12 (dd, 14.0, 14.0)
17.6 0.99 (s)
17.4 0.96 (s)
16.7 1.07 (s)
24.7 1.64 (s)
2.25 (dd, 5.0, 12.0)
68.7 4.28 (m)
85.6 3.55 (d, 9.5)
39.8
–
2
3
20
21
36.4
–
56.1 0.99 (m, overlapped)
19.0 1.36 (m), 1.54 (m)
33.6 1.50 (m), 1.65 (m)
28.9 1.28 (m,
overlapped)
28 177.0
–
4
44.0
–
1.75 (m,
overlapped)
40.7
47.9 1.90 (dd, 9.5, 9.5)
38.5
24.2 2.08 (m)
128.2 5.50 (t, 3.5)
–
29
30
1′
2′
3′
4′
5′
6′
27.0 1.38 (s)
17.0 1.06 (d, 7.0)
93.7 6.15 (d, 7.5)
79.3 4.42 (dd, 7.5, 8.5)
79.0 4.28 (dd, 8.5, 9.0)
70.9 4.20 (dd, 9.0, 9.0)
79.1 3.92 (m)
5
6
56.5 1.09 (m, overlapped)
19.3 1.42 (m, overlapped)
1.64 (m)
22
23
24
32.0 1.86 (m)
10
11
12
13
14
15
–
24.1 1.55 (s)
65.6 3.71 (d, 10.5)
4.44 (d, 11.5)
7
8
9
10
11
33.5 1.42 (m)
139.5
42.1
–
40.0
48.3 1.75 (m, overlapped)
38.3
24.2 1.97 (m)
–
25
26
27
17.3 0.99 (s)
17.4 1.10 (s)
26.1 1.22 (s)
–
29.8 1.36 (m, overlapped)
62.4 4.32 (dd, 6.0, 11.5)
4.40 (br. d, ca. 12)
–
2
1
.40 (ddd, 5.0, 14.5,
4.5)
28 176.6 –
12 122.7 5.45 (t, 3.0)
29
30
1′
2′
3′
73.7 3.56 (s)
19.7 1.09 (s)
95.8 6.32 (d, 8.0)
74.1 4.21 (dd, 8.0, 8.5)
78.9 4.30 (dd, 8.5, 9.0)
1
6
26.8 1.21 (m, overlapped)
1″ 104.8 5.64 (d, 7.5)
13 144.3
–
1.97 (m, overlapped)
14
15
42.1
–
17
18
19
20
21
48.6
–
2″
3″
4″
5″
6″
75.9 4.05 (dd, 7.5, 9.0)
78.3 4.20 (dd, 9.0, 9.0)
72.9 4.07 (dd, 9.0, 9.0)
78.1 3.97 (m)
63.9 4.34 (dd, 6.0, 12.0)
4.58 (dd, 3.0, 12.0)
28.3 1.17 (m, overlapped)
2.35 (ddd, 4.5, 14.0,
14.0)
54.5 2.89 (s)
72.7
–
42.2 1.44 (m)
25.9 2.23 (m, overlapped)
16
17
18
23.5 2.00 (m), 2.18 (m)
47.5
41.2 3.30 (dd, 4.0, 14.0)
4′
5′
6′
71.1 4.36 (dd, 9.0, 9.0)
79.3 4.04 (m)
62.2 4.40 (dd, 5.0, 12.0)
4.46 (dd, 2.0, 12.0)
–
3
1
.08 (ddd, 4.5, 13.0,
3.0)

Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
81
ion mode m/z 847.4210 [M + Cl]− (calcd for C42
47.4252).
H
O
15Cl
Table 6
68
1
H and 13C NMR data for 5 in CD
3
OD.
8
No.
δ
C
δ
H
(J in Hz)
No.
δ
C
H
δ (J in Hz)
2
.3.4. Officinoterpenoside C (4)
1
2
3
4
5
6
7
213.4
130.0
185.4
51.7
48.6
10.2
–
8
9
18.8
15.1
1.02 (s)
2.13 (s)
4.26 (d, 8.0)
3.13 (dd, 8.0, 9.0)
3.32 (dd, 9.0, 9.0)
3.27 (dd, 9.0, 9.0)
3.26 (m)
White powder. [α]2
5
+6.2° (c = 0.78, MeOH); IR νmax (KBr)
cm : 3367, 2932, 2840, 1732, 1648, 1559, 1457, 1267, 1072.
5.86 (d, 1.0)
–
D
1′
2′
3′
4′
5′
6′
104.3
74.8
78.1
71.5
77.9
62.7
−1
–
1
13
H NMR (500 MHz, CD
3
OD) and C NMR (125 MHz, CD
3
OD)
N) and
5 5
C NMR (125 MHz, C D N) spectroscopic data, see Table 5;
2.67 (q, 7.5)
1.05 (d, 7.5)
3.58 (d, 9.5)
1
spectroscopic data, see Table 4; H NMR (500 MHz, C
5 5
D
13
73.5
3
.92 (d, 9.5)
3.66 (dd, 5.0, 11.5)
HRESI-TOF-MS: Negative-ion mode m/z 711.3961 [M +
COOH] (calcd for C37
3
.87 (dd, 1.5, 11.5)
−
H
59
O
13 711.3938).
2
.3.5. Officinoterpenoside D (5)
2
5
White powder. [α]
D
+17.5° (c = 0.89, MeOH); IR νmax (KBr)
cm : 3503, 2931, 2867, 1674, 1602, 1560, 1454, 1422, 1320,
251, 1069, 1023; UV λmax (MeOH) nm (log ε): 312 (3.54), 265
25
White powder. [α]
D
−55.9° (c = 0.88, MeOH); IR νmax
−
1
−1
(
KBr) cm : 3382, 2970, 2916, 2877, 1690, 1618, 1434, 1381,
1
(
1
320, 1285, 1218, 1162, 1077, 1039, 860; UV λmax (MeOH) nm
3.97). 1H NMR (500 MHz, CD
OD) spectroscopic data, see Table 1; HRESI-TOF-MS:
Negative-ion mode m/z 671.2899 [M–H] (calcd for C32
13
3
OD) and C NMR (125 MHz,
1
13
(
3
log ε): 224 (4.11). H NMR (500 MHz, CD OD) and C NMR
CD
3
(
125 MHz, CD
3
OD) spectroscopic data, see Table 6; HRESI-TOF-
−
H O
47 15
−
MS: Negative-ion mode m/z 351.1225 [M + Cl] (calcd for
C H O Cl 351.1216).
15 24 7
6
71.2920).
2
.3.2. Officinoterpenoside A
2
(2)
−0.5° (c = 0.85, MeOH); IR νmax
KBr) cm : 3367, 2926, 2851, 1671, 1600, 1560, 1456, 1420,
364, 1327, 1255, 1221, 1071, 1016; UV λmax (MeOH) nm
2
.4. Acid hydrolysis of 1–5
2
5
White powder. [α]
D
−
1
(
1
1
A solution of officinoterpenosides A –D (1–5, 2.5 mg
each) in 1 M HCl (1 mL) was heated under reflux for 3 h,
respectively. The reaction mixture was neutralized with
Amberlite IRA-400 (OH form) and removed by filtration.
The aqueous layer was subjected to the HPLC analysis
under the following conditions, respectively: HPLC column,
1
(
3
log ε): 312 (3.54), 262 (3.88). H NMR (500 MHz, CD OD) and
1
3
C NMR (125 MHz, CD
3
OD) spectroscopic data, see Table 2;
−
−
HRESI-TOF-MS: Negative-ion mode m/z 671.2897 [M–H]
calcd for C32 15 671.2920).
(
47
H O
2
Kaseisorb LC NH -60-5, 4.6 mm i.d. × 250 mm (Tokyo Kasei
2
.3.3. Officinoterpenoside B (3)
Co. Ltd., Tokyo, Japan); detection, optical rotation [Chiralyser
(IBZ Messtechnik GMBH, Mozartstrasse 14–16 D-30173
Hannover, Germany)]; mobile phase, CH CN–H O (75:25,
3 2
v/v); and flow rate 1.0 mL/min. D-Glucose from 1–5 presented
2
5
White powder. [α]
D
−6.9° (c = 0.38, MeOH); IR νmax
−
1
(
KBr) cm : 3367, 2919, 2851, 1733, 1641, 1457, 1384, 1077.
1
13
H NMR (500 MHz, C
5 5
D N) and C NMR (125 MHz, C
5 5
D N)
spectroscopic data, see Table 3; HRESI-TOF-MS: Negative-
in the aqueous was carried out by comparison of its retention
Fig. 1. The new compounds (1–5) obtained from the aerial parts of R. officinalis.

82
Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
Fig. 2. The known terpenes (6–16) obtained from the aerial parts of R. officinalis.
time and optical rotation with that of authentic samples, t
R
(1S,4S,5S)-5-exo-hydrocamphor 5-O-β-D-glucopyranoside
(6), isorosmanol (7), rosmanol (8), 7-methoxyrosmanol (9),
epirosmanol (10), ursolic acid (11), micromeric acid (12),
1
7.6 min (positive).
oleanolic acid (13), niga-ichigoside F
1
(14), glucosyl tormentate
3
. Results and discussion
(15), and asteryunnanoside B (16). Among the known ones,
6
1
was isolated from the Rosmarinus genus first, and 15 and
6 were obtained from this species for the first time. The
The dried aerial parts of R. officinalis were refluxed with 95%
EtOH for 3 times. Evaporation of the solvent was done under
reduced pressure to yield the 95% ethanol extract. The extract
structures of the new compounds 1–5 and known ones were
shown in Figs. 1 and 2, respectively.
was partitioned in a CHCl
CHCl and H O partitions. Then, the H
D101 macroporous resin CC, and eluted sequentially with H
and 95% EtOH. CHCl partition and 95% EtOH eluate from
3 2
–H O mixture (1:1) to give both
Officinoterpenoside A
1
(1) was obtained as a white powder
3
2
2
O layer was subjected to
25
with positive optical rotation ([α]
molecular formula C32
ion HRESI-TOF-MS (m/z 671.2899 [M–H] , calcd for C32
6
hydroxyl (3503 cm ), α,β-unsaturated ketone (1674 cm ),
aromatic ring (1602, 1560, 1514, 1454 cm ), and an
D
+17.5° in MeOH). The
2
O
H
48
O
15 of it was determined by negative-
3
−
H O
47 15
D101 CC were subjected to normal- and reverse-phase CC, and
finally preparative HPLC (PHPLC) to give 16 terpenoids, which
71.2920). The IR spectrum of 1 suggested the presence of
−
1
−1
1 2
included five new ones, officinoterpenosides A (1), A (2),
−
1
B (3), C (4), and D (5), together with 11 known isolates,
Fig. 3. The main 1H 1H COSY and HMBC correlations of 1 and 2.

Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
83
O-glycosidic linkage (1069 cm−1). On acid hydrolysis and
NMR experiments including 1H 1H COSY, HSQC, HMBC, and
identification with HPLC analysis, the presence of D-glucose
NOESY spectra suggested that 2 had same aglycon as 1 and two
was determined [25]. The 13C NMR (CD
OD, Table 1) spectrum
displayed 32 carbons including 20 carbons for the aglycon, and
2 carbons for two sugar units. The carbon type for 20 carbons
β-D-glucopyranosyl moieties [δ
4.56 (1H, d, J = 8.0 Hz, H-1″)]. According to the long-range
correlations between δ 4.35 (H-1′) and δ 89.6 (C-3), and
4.56 (H-1″) and δ 150.6 (C-12) observed in the HMBC
3
H
4.35 (1H, d, J = 8.5 Hz, H-1′),
1
H
C
in aglycon of 1 was determined by DEPT experiment,
δ
H
C
which sorted by 4 methyls, 4 methylenes, 4 methines, and
experiment, the linkages of two D-glucose were determined.
8
1
1
quaternary carbon signals. Among them, δ
C
122.2 (C-14),
Consequently, the structure of 2 was identified, and named as
29.6 (C-8), 132.5 (C-13), 140.8 (C-9), 148.8 (C-11), and
50.2 (C-12) revealed the presence of a penta-substituted
officinoterpenoside A
2
.
Officinoterpenoside B (3) was isolated as a white powder
1
1
25
aromatic ring. Meanwhile, in the H- H COSY experiment, the
correlations between δ [1.27 (1H, ddd, J = 3.0, 13.5, 13.5 Hz),
.31 (1H, m), H -1] and δ 1.67, 1.76 (1H each, both m, H -2);
1.67, 1.76 (H -2) and δ 3.18 (1H, dd, J = 4.5, 11.5 Hz, H-3);
1.69 (1H, dd, J = 3.0, 14.0 Hz, H-5) and δ [2.58 (1H, dd, J =
.0, 17.0), 2.62 (1H, dd, J = 14.0, 17.0), H -6]; δ
.30 (1H, dd, J = 6.0, 13.0 Hz), H -15] and δ
4.16 (H-16) and δ
with negative rotation [[α]
molecular formula was determined to be
negative-ion HRESI-TOF-MS (m/z 847.4210 [M + Cl] , calcd
for C42 15Cl 847.4252). The IR spectrum showed absorption
bands at 3367, 1733, and 1641 cm
carboxyl, and olefin functions, respectively. The 1H NMR
(C N, Table 3) spectrum of 3 showed signals assignable to
seven methyls [δ 0.96, 0.99, 1.07, 1.17, 1.38, 1.64 (3H each, all s,
-25, 24, 26, 23, 29, 27), 1.06 (3H, d, J = 7.0 Hz, H -30)], two
D
−6.9° (c = 0.38, MeOH)]. Its
H
42 68
C H O15 by
−
3
2
H
2
δ
δ
H
2
H
68
H O
−
1
H
H
ascribable to hydroxyl,
3
3
2
H
[2.63 (1H, m),
4.16 (1H, m,
2
H
5 5
D
H-16); δ
H
H 3
1.18 (3H, d, J = 6.5 Hz, H -17)
were observed, which indicated the presence of partial
structure written in bold lines (Fig. 3). In the HMBC
experiment, the long-range correlations were observed be-
tween the following proton and carbon pairs: H-14 and C-9, 12;
H
H
Furthermore, the relative configurations of rings A and B were
elucidated by NOESY experiment. The NOE correlations were
observed between δ
H
3
3
methines bearing oxygen function [δ 3.32 (1H, d, J = 9.5 Hz,
H-3), 4.03 (1H, m, H-2)], one tri-substituted olefin [δ 5.50
(1H, t, J = 3.5 Hz, H-12)], together with two anomeric proton
signals [δ 5.64 (1H, d, J = 7.5 Hz, H-1″), δ 6.15 (1H, d, J = 7.5 Hz,
H-1′)]. The 13C NMR spectrum displayed 42 carbons including
30 carbons for the aglycon, and 12 carbons for two sugar units.
2 3 3
-15 and C-12–14; H -17 and C-15, 16; H -18 and C-3–5, 19;
3 3
-19 and C-3–5, 18; and H -20 and C-1, 5, 9, 10 (Fig. 3).
1
13
H and C NMR spectra suggested that 3 was an ursolic acid
type triterpene saponin derivative. In conjunction with the
H
1.67 (H
3.18 (H-3) and δ
1.69 (H-5) and δ
2.58 (H -6) and δ
-19) and δ 1.40 (H
β
-2) and δ
1.27 (H -1), 1.02 (H
1.27 (H -1), 2.62 (H
0.92 (H -19), 1.40 (H
-20), which suggested that the
H
0.92 (H
3
-19), 1.40
-18), 1.69
-6), 1.02
-20);
1
13
(
(
(
H
3
-20); δ
H-5); δ
-18); δ
0.92 (H
H
H
α
3
analysis of the HSQC spectrum, H and C NMR data for 3 were
1
1
H
H
α
α
assigned as shown in Table 3. The H H COSY experiment on
3 indicated the presence of partial structure written in bold
lines. And in HMBC experiment, long-range correlations were
observed between the following proton and carbon pairs: H-18
H
3
H
β
H
3
3
δ
H
3
H
3
relative configuration of 1 was as shown in Fig. 4 with the
abietane skeleton. Furthermore, the linkages of two D-glucose
were determined by the observed long-range correlations
between δ
and δ 4.86 (1H, d, J = 8.0 Hz, H-1″) and δ
basis of the above-mentioned evidence, the structure of 1 was
elucidated, and named as officinoterpenoside A
Officinoterpenoside A (2) was also isolated as a white
and C-20, 28; H
and C-1, 5, 9, 10; H
-29 and C-18–20; H
3
3
-23 and C-3–5, 24; H
-26 and C-7–9, 14; H
-30 and C-19–21; H-1′ and C-28; H-1″
3
-24 and C-3–5, 23; H
3
-25
3
3
-27 and C-8, 13–15;
H
4.74 (1H, d, J = 8.0 Hz, H-1′) and δ
C
150.2 (C-12),
H
3
H
C
82.9 (C-2′). On the
and C-2′ (Fig. 5). On the basis of the above mentioned evidence,
the planar structure of 3 was determined, which was the same
1
.
2
powder. The molecular formula was the same as that of 1,
which was determined by negative-ion HRESI-TOF-MS (m/z
−
6
71.2897 [M–H] , calcd for C32
47
H O15 671.2920), too. From the
acid hydrolysis of 2 with 1.0 M HCl, D-glucose was given, which
was identified by HPLC analysis using an optical rotation
1
13
detector [25]. The H (500 MHz) and C NMR (125 MHz)
(
3
CD OD, Table 2) spectra of 2, which were assigned by various
Fig. 4. The main NOE correlations for aglycon of 1 and 2.
Fig. 5. The main 1H 1H COSY and HMBC correlations of 3.

84
Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
Fig. 6. The main 1H 1H COSY, HMBC and NOE correlations of 4.
as pruvuloside A [22] with 2α,3α,19α-trihydroxyl groups. But
the 13C NMR data in 1–5 positions of 3 [δ 48.0 (C-1), 68.6 (C-2),
C
oxymethylene group (δ 74.3) in ring E. Finally, the relative
configuration for 4 was determined by NOESY experiment,
8
3.9 (C-3), 39.8 (C-4), 56.1 (C-5)] were significantly different
from those of pruvuloside A [δ 43.0 (C-1), 66.2 (C-2), 79.1
C-3), 38.7 (C-4), 48.7 (C-5)] [22], which suggested that the
which showed NOE correlations between the following proton
pairs: H-2 and H
2
-24, H
-23; H-12 and H-18, H
-25; and H -25 and H -26. Furthermore, the chemical shifts
N) were
in accordance with those of known sericoside compounds with
2α,3β,24-OH [δ 24.4 (C-23), 56.4 (C-5), 65.4 (C-24), 85.7
3
-25; H-3 and H-5, H
3
-23; H-5 and
(
H
H
3
3
-26; H-18 and H -30; H
3
2
-24 and
configuration of hydroxyl groups at 2,3-position for the two
compounds was not the same as each other. Meanwhile, the
coupling constant (J = 9.5 Hz) between H-2 and H-3 of
3
3
3
5 5
of 3, 5, 23, and 24-positions in ring A (Table 5, in C D
3
indicated that hydroxyl groups at 2,3-position mutually trans
C
configuration. On the other hand, the proton and carbon signals
(C-3)] [26], but different from those of quadranoside IV
(2α,3β,23-trihydroxyurs-12-en-28-oic acid β-glucopyranosyl
1
13
in the H and C NMR spectra of 3 were very similar to those of
glucosyl tormentate (15) [23], except for the signals due to
another β-D-glucopyranosyl part. Finally, acid hydrolysis of it
yielded D-glucose, which was identified by retention time and
optical rotation using chiral detection by HPLC analysis [25].
On the basis of the above mentioned evidence, the structure of
ester) [δ
In addition, comparison of the C NMR signals for 29 and
30-positions in 4 [δ 19.7 (C-30), 73.7 (C-29)] with those of
C
14.4 (C-24), 48.2 (C-5), 66.5 (C-23), 78.2 (C-3)] [27].
1
3
C
3α,29-dihydroxy-23-oxo-olean-12-en-28-oic acid-28-O-α-
L-rhamnopyranosyl(1 → 4)-β-D-glucopyranosyl(1 → 6)-β-
3
was characterized to be officinoterpenoside B.
C
D-glucopyranosyl ester [δ 19.7 (C-30), 73.6 (C-29)] and
Officinoterpenoside C (4) was isolated as a white amor-
3α,30-dihydroxy-23-oxo-olean-12-en-28-oic acid-28-O-α-
L-rhamnopyranosyl(1 → 4)-β-D-glucopyranosyl(1 → 6)-β-
25
D
phous powder having a positive rotation [[α] +6.2° (c =
0
.78, MeOH)]. The molecular formula of 4 was determined to
C
D-glucopyranosyl ester [δ 28.2 (C-29), 65.4 (C-30)] [28], the
be C36
H
58
O
11 by negative-ion HRESI-TOF-MS (m/z 711.3961
relative configuration of hydroxymethyl group at 20-position
was determined as α. The acid hydrolysis experiment gave
D-glucose as the sugar moiety [25]. Consequently, the structure
of officinoterpenoside C was elucidated as (4) 2α,3β,24,29-
tetrahydroxyolean-12-en-28-oic acid-28-O-β-D-glucopyranosyl
ester.
−
[
M + COOH] , calcd for C37
59
H O13 711.3938). The IR spectrum
of 4 indicated the presence of hydroxyl, carboxyl, and olefinic
groups. The H and C NMR (CD
1
13
3
OD, Table 4) spectrum of
4
suggested that it was a triterpene monoglycoside with an
1
1
oleanane skeleton. The H H COSY experiment on 4 indicated
the presence of partial structure written in bold lines. The long-
range correlations (Fig. 6) observed in HMBC experiment
Officinoterpenoside D (5) was obtained as a white powder
with a negative rotation [[α]2
5
−55.9° (c = 0.88, MeOH)]. It
D
indicated that there were two oxymethine groups (δ
C
69.6,
had the molecular formula, C15
negative-ion HRESI-TOF-MS (m/z 351.1225 [M + Cl] , calcd for
H
24
O
7
as deduced from the
−
8
5.9) and an oxymethylene group (δ 66.2) in ring A, and an
C
Fig. 7. The main 1H 1H COSY, HMBC and NOE correlations of 5.

Y. Zhang et al. / Fitoterapia 99 (2014) 78–85
85
Cl 351.1216). The IR absorption band at 1690 cm−1
15 24 7
C H O
and the characteristic UV maxima absorption at 224 nm (4.11)
[7] Bakirel T, Bakirel U, Keles OU, Ulgen SG, Yardibi H. In vivo assessment of
antidiabetic and antioxidant activities of rosemary (Rosmarinus officinalis)
in alloxan-diabetic rabbits. J Ethnopharmacol 2008;116:64–73.
revealed the presence of an α,β-unsaturated ketone group in 5.
[8] González-Trujano ME, Peña EI, Martínez AL, Moreno J, Guevara-Fefer P,
Déciga-Campos M, et al. Evaluation of the antinociceptive effect of
Rosmarinus officinalis L. using three different experimental models in
rodents. J Ethnopharmacol 2007;111:476–82.
[9] Nogueira de Melo GA, Grespan R, Fonseca JP, Farinha TO, Silva EL, Romero
AL, Bersani-Amado CA, Cuman RK. Rosmarinus officinalis L. essential oil
inhibits in vivo and in vitro leukocyte migration. J Med Food 2011;14:
1
On the acid hydrolysis, D-glucose was yielded [25]. The H NMR
and 1 C NMR (CD
3
3
OD, Table 6) spectra of it showed signals
-8,
-6)], one methene bearing oxygen
function [δ 3.58, 3.93 (1H each, both d, J = 9.5 Hz, H -7)], one
methine bearing methyl group [δ 2.67 (1H, q, J = 7.5 Hz, H-5)],
one α,β-unsaturated ketone moiety [δ 5.86 (1H, d, J = 1.0 Hz,
H-2); δ 130.0 (C-2), 185.4 (C-3), 213.4 (C-1)], together with a
ascribable to three methyls [δ 1.02, 2.13 (3H each, both s, H
), 1.05 (3H, d, J = 7.5 Hz, H
3
9
3
2
944–9.
[
10] Huang SC, Ho CT, Lin-Shiau SY, Lin JK. Carnosol inhibits the invasion of
B16/F10 mouse melanoma cells by suppressing metalloproteinase-9
through down-regulating nuclear factor-kappa B and c-Jun. Biochem
Pharmacol 2005;69:221–32.
11] Pérez-Fons L, Garzón MT, Micol V. Relationship between the antioxidant
capacity and effect of rosemary (Rosmarinus officinalis L.) polyphenols on
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12] Escop M. Rosmarini folium. The scientific foundation for herbal medicinal
products. Thieme Med Pub2nd ed. ; 2009 429–36.
H
C
β-D-glucopyranosyl group [δ 4.26 (1H, d, J = 8.0 Hz, H-1′)].
In HMBC experiment, long-range correlations were observed
between the following proton and carbon pairs: H-2 and C-1,
[
[
3 2 3
3–5; H -6 and C-1, 4, 5; H -7 and C-4, 5, 8; H -8 and C-3–5, 7;
H
3
-9 and C-2–4 (Fig. 7). On the basis of the above-mentioned
[13] Cuvelier ME, Richard H, Berset C. Antioxidative activity and phenolic
composition of pilot-plant and commercial extracts of sage and rosemary.
J Am Oil Chem Soc 1996;73:645–52.
evidence, the planar structure of 5 was determined as shown
in Fig. 7. Furthermore, on the NOESY experiment, the NOE
correlations between the following proton pairs: H-2 and H
[
14] Cuvelier ME, Berset C, Richard H. Antioxidant constituents in sage (Salvia
officinalis). J Agric Food Chem 1994;42:665–9.
3
-8,
[
15] Kim KH, Choi JW, Choi SU, Lee KR. Terpene glycosides and cytotoxic
constituents from the seeds of Amomum xanthioides. Planta Med 2010;76:
H
3
-9; H-5 and H -7; H -8 and H -6, H -9 were observed, which
2
3
3
3
suggested that 5 has 2Z,3S*,4S* configuration. Consequently,
the structure of officinoterpenoside D was elucidated, which is
a normonoterpenoid glycoside.
461–4.
[16] Nakatani N, Inatani R. Two antioxidative diterpenes from rosemary
(Rosmarinus officinalis L.) and a revised structure for rosmanol. Agric Biol
Chem 1984;48:2081–5.
[
17] Arisawa M, Hayashi T, Ohmura K, Nagayama K, Shimizu M, Morita N, et al.
Chemical and pharmaceutical studies on medicinal plants in Paraguay:
studies on Romero, part 2. J Nat Prod 1987;50:1164–6.
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This research was supported by the Program for New
Century Excellent Talents in University (NCET-12-1069) and
the Program for Tianjin Innovative Research Team in University
(
TD12-5033).
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