j nat. prod. 2006, 69, 338-341 cytotoxic xenia diterpenoids from the soft coral xenia umbellata ali...
TRANSCRIPT
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Ali A. El-Gamal, Shang-Kwei Wang and Chang-Yih Duh
Department of Marine Biotechnology and Resources,
National Sun Yat-sen University, Kaoshiung, Taiwan,
Republic of China,
Faculty of Pharmacy, Mansoura University, Egypt
&
Department of Microbiology,Kaoshiung Medical University,
Kaoshiung, Taiwan, Republic of China
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Abstract
Eleven new diterpenoids, umbellacins
A-G (1-7), 14,15-epoxy-xeniolide H (8), 3-
acetyl-14,15- epoxy-xeniolide H (9), and
umbellacins H and I (11, 12), were isolated
from a methylene chloride-soluble frations
of the soft coral Xenia umbellata. The
structures were elucidated by extensive
spectroscopic analysis, and their cytotoxicity
against selected cancer cells was measured
in vitro.
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The soft coral Xenia umbellata was studied
because CH2Cl2 showed significant
cytotoxicity to A549 (human lung
adenocarcinoma), HT-29 (human colon
adenocarcinoma) and P388 (mouse
lymphocytic leukaemia). The aim of this
study will deals with separation, structural
elucidation and biological study of some
cytotoxic xenicane-type diterpenooids
characteristic for xenia umbellata.
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A photo of Xenia
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A photo of Xenia
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Bodies of the soft coral X. umbellata were freeze-dried to give 800 g of a solid
extract with CH2Cl2 (3LX3), conc in vacum
60 g of CH2Cl2 extract
CC, Sil. gel using n-hex. and n-hex. -EtOAc gradient, followed byEtOAc-MeOH, gradient
%of EtOAc/n-Hex
10% 17% 20% 50%40%
%of MeOH/EtOAc
2% 5%
9 8 1 6,10,115 2,4
HPLC (Rp-18), MeOH-H2O (65:35)
HPLC (Rp-18), MeOH-H2O (60:40)
HPLC (Rp-18), MeOH-H2O
3 7
HPLC (Rp-18), MeOH-H2O (60:40)
HPLC (Rp-18), MeOH-H2O (68:32)
HPLC (Rp-18), MeOH-H2O (73:27)
HPLC (Rp-18), MeOH-H2O (82:18)
Sub Fr.. A Sub Fr.. B Sub Fr.. C Sub Fr.. D Sub Fr.. E Sub Fr.. FSub Fr.. G
%of MeOH/H2O
70% 67%
Compounds 2, 4, 5, 6, 10, and 11 exhibited cytotoxicityagainst P-388 lymphocytic leukemia with ED50values of 1.6, 4.2, 3.8, 3.7, 3.4, and 3.6g/m, respectively., none of the isolates were cytotoxic to A549 (human lung adenocarcinoma)and HT-29 (human colon adenocarcinoma) cell lines (IC50> g/mL).
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Isolated Xenicane Diterpenoids from Soft Coral Xenia umbellata
OH
H
1
34
5 6
7
9
10
4a
11a
1213
1415
16
17
18
H 11
Umbellacin F (6)
O
MeO
AcO
19
HO
8
Umbellacin G (7)
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
R = H, 14,15-epoxy Xenolide H (8)R= Ac, 3- acetyl 14,15-epoxy- Xenolide H (9)
O
O
RO
OH
O
3
Umbellacin H (10)19
H
1
4
5 6
7
8
910
11a
1213
1415
16
17
18
19
H 11
OH
O
MeO
O
O
3
HO
OH
OH
OH
H
34
5 6
7
89
10
4a
11a
1213
1415
16
17
18
19
H 11
Umbellacin I (11)
O
MeO
AcO
HO
OH
O
OMe
H
1
34
5 6
7
89
10
4a
11a
1213
14 15
16
17
1819
H
MeO
OH
OH
O
OH
O
OH
H
1
3 4
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
Umbellacin C (3)
OHC
OHC
OH
OH
H
1
34
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
Umbellacin A (1)
OH
OH
OH
H
34
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
Umbellacin B (2)
OHO
MeO
AcO
OH
OH
H
34
5 6
7
89
10
4a
11a
1213
1415
16
17
18
19
H 11
Umbellacin E (5)
O
MeO
AcO
HO9
Umbellacin D (4)
OH
H
1
34
4a
11a
1213
1415
16
17
H
O
MeO
AcO
O
H
5
6
7
8
10
11
19
18
HO
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OHC
OHC
OH
OH
H
1
34
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
OH
1 313
1214
8
1617
18
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1HNMR of Compound 2 (Umbellacin B)
12
17173
OH
H
34
5 6
7
89
10
4a
11a
1213
1415
17
16
18
19
H 11
OHO
MeO
AcO
HO
14
OMe
8
4a 11a13
OAc
16 18
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H HCOSY of Compound 2 (Umbellacin B)
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HSQC of Compound 2 (Umbellacin B)
OH
H
34
5 6
7
89
10
4a
11a
1213
1415 16
17
18
19
H 11
OHO
MeO
AcO
HO
HSQC of Compound 2 (Umbellacin B)
12 17 3 14OMe
8 4a 11a 13
OAc 16 18
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1HNMR of compound 3 (umbellacin C)
O
OH
O
OH
H
1
3 4
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
131210
14
3
3
811a
9
1617
18
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1H1 H COSY of Compound 3 (Umbellacin C)
O
OH
O
OH
H
1
3 4
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
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13C NMR of Compound 3 (Umbellacin C)
O
OH
O
OH
H
1
3 4
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
114
114
12 10 13
3
158 11a 4a
7
196
9
1617
5 18
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HSQC of Compound 3 (Umbellacin C)
O
OH
O
OH
H
1
3 4
5 6
7
89
10
4a
11a
1213
14 15
16
17
18
19
H 11
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HMBC of Compound 3 (Umbellacin C)
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1H NMR of compound 4 (Umbellacin D)
123
9
OH
H
1
34
4a
11a
1213
1415
16
17
H
O
MeO
AcO
O
H
5
6
7
8
10
11
19
18
HO
8
19
19 4a 11a
OMe
OAc
1617 18
13
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Expanded 13C NMR and DEPT Experiment of Compound 4 (Umbellacin D)
8 14 1915 3 OMe 7 11 11a 4a 13
OAc18
9
OH
H
1
34
4a
11a
1213
1415
16
17
H
O
MeO
AcO
O
H
5
6
7
8
10
11
19
18
HO
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HSQC of Compound 4 (Umbellacin D)
9
OH
H
1
34
4a
11a
1213
1415
16
17
H
O
MeO
AcO
O
H
5
6
7
8
10
11
19
18
HO
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1HNMR of Compound 6 (Umbellacin F)
12 8
193
OMe
14
4a 11a13
OAc
18 1617
OH
H
1
34
5 6
7
9
10
4a
11a
1213
1415
16
17
18
H 11O
MeO
AcO
19
HO
8
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13C NMR of compound 6 (Umbellacin F)
OH
H
1
34
5 6
7
9
10
4a
11a
1213
1415
16
17
18
H 11O
MeO
AcO
19
HO
8
1 OAC 11 4 7 12819
15 3 14 11a OMe 9 4a
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O
OMe
H
1
34
5 6
7
89
10
4a
11a
1213
14 15
16
17
1819
H
MeO
OH
OH
1HNMR of compound 7 (umbellacin G)
13 12 14
38 19
919
1
OMe OMe
4a
18
1617
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1H NMR of Compound 8 (14,15-epoxy xeniolide H)
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
O
O
HO
OH
O
3
12,13 19
3
11a3’
148
94a 5
18
1617
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COSY of Compound 8 (14,15-epoxy xeniolide H)
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
O
O
HO
OH
O
3
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13 CNMR of Compound 8 (14,15-epoxy xeniolide H)
1 11 13 12 19
4 3 8 14
15 11a 4a
6 18 1617
9 5 107
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HMBC of Compound 8 (14,15-epoxy xeniolide H)
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NOESY Experiment of Compound 8 (14,15-epoxy xeniolide H)
12,13
19
311a,3’
14
84a9
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1H NMR of Compound 9 (3-acetyl 14,15-epoxy xeniolide H)
12,13
19
3
1411a8,4a,10
OAc
X
96
5 10
181617
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
O
O
AcO
OH
O
3
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1H 1H COSY of Compound 9 (3-acetyl 14,15-epoxy xeniolide H)
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
O
O
AcO
OH
O
3
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Expanded 1H HCOSY of Compound 9 (3-acetyl 14,15-epoxy xeniolide H)
1411a
8 4a
10
965
10
18
16 1
7
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13C NMR of Compound 9 (3-acetyl 14,15-epoxy xeniolide H)
1 OAc 11
13
1219
4
38
1415
7
11a4a
6 91618
OAc
10517
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HSQC of Compound 9 (3-acetyl 14,15-epoxy xeniolide H)
H
1
4
5 6
7
8
910
11a
1213
14 15
16
17
18
19
H 11
O
O
AcO
OH
O
3
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1H NMR of Compound 10 (Umbellacin H)
12 19 19
3
OMe
14 4a11a
8
OAc 18
16 17
19
H
1
4
5 6
7
8
910
11a
1213
1415
16
17
18
19
H 11
OH
O
MeO
O
O
3
HO
OH
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1H NMR of Compound 11 (Umbellacin I)
OH
OH
H
34
5 6
7
89
10
4a
11a
1213
1415
16
17
18
19
H 11O
MeO
AcO
HO
OH
12 3
OMe
14
8
4a11a
OAc 16, 17
18
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13C NMR of Compound 11 (Umbellacin I)
OH
OH
H
34
5 6
7
89
10
4a
11a
1213
1415
16
17
18
19
H 11O
MeO
AcO
HO
OH
1 OAc 4 12 3 11aOMe 811 15 1
9 4a
7 13,5,18