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Natural Product Communications
Stereochemistry and NMR Data Assignment of Cyclopeptide Alkaloids from Zizyphus oxyphylla
2010 Vol. 5 No. 8 1205 - 1208
Muhammad Nisara∗, Waqar Ahmad Kaleemb, Achyut Adhikaric, Zulfiqar Alic, Nusrat Hussainc, Inamullah Khanb, Mughal Qayumb and M. Iqbal Choudharyc a
Institute of Chemical Sciences, University of Peshwar, Peshwar-25120, Pakistan
b
Department of Pharmacy, University of Peshwar, Peshwar -25120, Pakistan
c
International Center for Chemical and Biological Sciences, H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
[email protected] Received: April 20th, 2010; Accepted: June 7th, 2010
The structures of (3S,7R,13S)-6-[2-(dimethylamino)-3-phenylpropanoyl]-19-methoxy-2-oxa-6,9,15-triazatetracyclo[16.3.1.03,7. 09,13]docosa-1-(22),16,18,20-tetraene-8,14-dione (1), nummularin-C (2) and nummularin-R (3) have been previously determined mainly based on mass spectrometric data. Stereochemistry and complete 1H and 13C NMR spectroscopic data assignments of these compounds are now described. Compounds 1 and 2 are reported for the first time from Zizyphus oxyphylla. Keywords: Zizyphus oxyphylla, cyclopeptide alkaloids, NMR data assignment.
Zizyphus (Rhamnaceae) consists of about 100 species, of which six are indigenous to Pakistan [1a]. Various species of Zizyphus have been used in folk and the ayurvedic system of medicines for disorders such as fever, skin infections, urinary troubles, and diabetes [1b,1c]. Different biological activities such as antinociceptive and antipyretic [2a,2b], antioxidant and antilisterial [2c], larvicidal [2d] and antidiabetic [2e] have been reported for various species of Zizyphus. Previously, one cyclopeptide alkaloid (3) was reported from Zizyphus oxyphylla Edgew [3a]. ( 3 S , 7 R , 1 3 S ) - 6 - [ 2 - ( D i me t h yl a m i n o ) - 3 - p h e n y l propanoyl]-19-methoxy-2-oxa-6,9,15-triazatetracyclo [16.3.1.03,7.09,13] docosa-1-(22),16,18,20-tetraene-8,14dione (1), nummularin-C (2) and nummularin-R (3) have been reported previously from different Zizyphus species. Their structures were determined mainly on the basis of mass spectrometry [3a-3e]. This manuscript deals with the confirmation of the structures and complete 1H and 13C NMR spectroscopic data assignments of these compounds (Figure1). Compounds 1 and 2 are reported for the first time from this species. HRESI-MS of 1 displayed a quasi-molecular ion [M + H]+ at m/z 533.2323, which, in combination with
13
C NMR spectroscopy, suggested the molecular formula of C30H36N4O5 (calcd for C30H36N4O5 + H = 533.1763). The EI-MS spectrum showed a base peak at m/z 148, which indicated the presence of N, N-dimethyl phenylalanine as a side chain [4]. In the 1H NMR spectrum, a 6H methyl singlet at δ 2.38 was assigned to N, N-dimethyl protons. Methine resonances at δ 3.25 (dd, J5, 15 = 10.5 Hz, J5, 15′ = 5.5 Hz), 3.50 (dd, J22, 23 = 10.0 Hz, J22, 23′ = 3.5 Hz), 4.40 (d, J8,9 = 5.5 Hz) and 5.12 (m) were assigned to H-5, H-22, H-8 and H-9, respectively. Two olefinic protons resonating at δ 5.86 (d, J1, 2 = 8.5 Hz) and 6.80 (dd, J2, 1 = 8.5 Hz, J2,3 = 7.5 Hz) were attributed to H-1 and H-2, respectively. Aromatic protons at δ 6.75 (d, J12, 12′ = 3.0 Hz), 6.83 (dd, J12′, 13′ = 9.0 Hz, J12′, 12 = 3.0 Hz), and 6.98 (d, J13′, 12′ = 9.0 Hz) were ascribed to H-12, H-12′ and H-13′, respectively. Another five resonances between δ 7.12 - 7.20 were due to the phenyl protons of phenylalanine. In the 1H-1H COSY spectrum (Figure 2), the resonance at δ 6.80 (H-2) showed cross peaks with the resonances at δ 5.86 (H-1) and δ 8.38 (NH-3). The resonance of H-5 (δ 3.25) correlated with H2-15 (δ 1.91, 2.15), which in turn showed correlations with H2-16 (δ 1.51, 1.92), and the spin system was further extended to H2-17 (δ 3.44, 4.50). This spin system confirmed proline (A) as the amino acid of the
1206 Natural Product Communications Vol. 5 (8) 2010
Nisar et al.
13'
13'
13'
OMe
12'
OMe
12'
10
O
H
H
20
7
N
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24
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27
6
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H N Me
Me
26'
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11
H
H
N20
19
O 22
15
25 26
24
25'
27 26'
1
7 6
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5
H
O
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HN
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9
18
2
N3
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17
22
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17'
32
27
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Me
13 12
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H
O 6
N
O
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1 11
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9
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9
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1 11
14
14
14
OMe
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H H N Me
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H O 5
16 15
16'
17
Me
31 29
2
3
Figure 1: Structures of compounds 1-3. Table 1: 1H and 13C NMR spectroscopic data of compounds 1, 2 and 3 (δ, ppm, acetone-d6, 600 and 150 MHz respectively). C. No. 1 2 3 4 5 6 7 8 9 11 12 12′ 13 13′ 14 15 16 16′ 17 17′ 18 19 21 22 23 24 25 25′ 26 26′ 27 28 29 30 31 32 OCH3 N(CH3)2
1 δC 107.1 122.3 168.4 45.5 170.3 63.3 80.0 152.3 111.8 117.6 125.0 114.7 152.0 29.8 25.9 48.7 33.4 45.5 172.4 67.9 30.6 140.4 130.1 130.1 128.9 128.9 126.6 56.2 41.5
δH (J, Hz) 5.86 d (8.5) 6.80 dd (8.5, 10.5) 8.38 d (10.5) 3.25 dd (10.5, 5.5) 4.40 d (5.5) 5.12 m 6.75 d (3.0) 6.83 dd (9.0, 3.0) 6.98 d (9.0) 1.91 m, 2.15 m 1.51 m, 1.92 m 3.44 m, 4.50 m 2.13 m, 2.39 m 3.23 m, 4.14 m 3.50 dd (10.0, 3.5 ) 2.78 dd (10.0, 9.5 ), 3.10 dd (9.5, 3.5) 7.12 d (7.0) 7.12 d (7.0) 7.19 t (7.0) 7.19 t (7.0) 7.20 t (7.0) 3.77 s 2.38 s
2 δC 107.6 122.5 169.5 54.4 170.8 66.2 78.5 152.0 112.5 118.0 125.4 114.6 152.2 40.6 25.3 21.6 23.7 33.2 46.5 170.9 68.3 31.0 140.45 130.0 130.0 129.0 129.0 126.7 56.3 41.5
macrocyclic ring. Similarly, the resonance of H-8 (δ 4.40) showed, in turn, cross peaks with H-9, H2-18 and H2-19, which revealed another proline (B) ring in the molecule. The 13C NMR and DEPT spectra displayed resonances for thirty carbons (Table 1), including three methyl, six methylene, fourteen methine and seven quaternary carbons. The HMBC correlations were used to join different spin systems and functionalities of the molecule (Figure 3).
δH (J, Hz) 5.87 d ( 9.0) 6.81 dd ( 9.0, 10.5) 8.92 d (10.5) 4.27 m 7.80 d ( 6.5) 4.42 d (2.5) 5.24 m 6.81 (3.0) 6.74 dd (8.7, 3.0) 6.97 d (8.7) 2.65 m, 2.84 m 1.87 m 0.90 d (6.5) 0.98 d (6.5) 2.12 m, 2.42 m 3.22 m, 4.50 m 3.61 dd (10.0, 3.5) 2.82 dd (10.0, 9.5), 3.11 dd (9.5, 3.5) 7.18 bd (7.0) 7.18 bd (7.0) 7.16 t (7.0) 7.16 t (7.0) 7.12 t (7.0) 3.77 s 2.37 s
3 δC 107.6 122.4 168.7 60.8 171.5 65.9 78.5 152.2 112.5 117.9 125.5 114.5 152.1 36.6 25.7 16.4 11.9 33.3 46.5 171.3 66.9 20.4
δH (J, Hz) 5.86 d (9.0) 6.85 dd (10.8, 9.0) 8.96 d (10.8) 4.18 t (6.6) 7.85 d (6.6) 4.54 d (3.0) 5.24 m 6.79 d (3.0) 6.75 dd (9.0, 3.0) 6.95 (9.0) 1.92 m 1.19 m, 1.45 m 0.92 d (6.6) 0.83 t (7.20)
112.1 128.5
2.11m, 2.40 m 3.17 m, 4.09 m 3.71 dd (10.2, 3.0) 3.02 dd (13.8, 3.0), 3.23 dd (13.8, 10.2) -
118.9
7.55 d (7.5)
119.4 122.0 112.1 137.5 123.9 56.3 41.7
6.99 t (7.5) 7.06 t (7.5) 7.33 d (7.5) 10.05 br s 6.90 br s 3.77s 2.44 s
Stereochemistry in 1 was determined with the help of coupling constant values and the NOESY spectrum. The resonance of H-12 showed cross peaks with NH-3, while H-8 showed correlations with both methylene protons of C-17. Key NOESY correlations of compound 1 are shown in Figure 2. Compound 2, an amorphous solid, displayed a quasimolecular ion [M + H]+ at m/z 549.2664 in the HRESIMS, which was in accordance with the molecular
NMR assignments of cyclopeptide alkaloids
Natural Product Communications Vol. 5 (8) 2010 1207
Figure 2: Key COSY and NOESY interactions in compounds 1-3.
Figure 3: Key HMBC interactions in compounds 1-3.
formula of C31H40N4O5 (calcd for C31H40N4O5 + H = 549.3076). The EI-MS showed a base peak at m/z 148, which indicated the presence of N, N-dimethyl phenylalanine as a side chain [4]. When the NMR spectroscopic data of 2 were compared with those of 1, the resonances for proline (A) were found to be missing, showing instead a leucine amino acid unit (Table 1). Compound 3, an amorphous solid displayed a quasimolecular ion [M + H]+ at m/z 588.2789 in the HRESIMS, corresponding to the molecular formula of C33H41N5O5 (calcd for C33H41N5O5 + H = 588.3185). The EI-MS showed a base peak at m/z 187, which indicated the presence of N, N-dimethyl tryptophan as a side chain [3d]. When the NMR spectroscopic data of 3 were compared with those of 1, the resonances for proline (A) and N, N- dimethyl phenylalanine were found to be missing, showing instead signals for isoleucine and N, N- dimethyl tryptophan units (Table 1). The 1H and 13C NMR assignments of 2 and 3 (Table 1) were based on 1H-1H COSY (Figure 2), HSQC and HMBC (Figure 3) spectra. Stereochemistry in
compounds 2 and 3 were assigned in a similar manner to that of 1 (Figure 2).
Experimental General experimental procedures: UV spectra were recorded on a Schimadzu UV-240 spectrometer in MeOH. IR spectra were obtained as KBr discs on a JASCO A-302 spectrophotometer. 1H and 13C NMR (600 MHz and 125 MHz) spectra were recorded in C3D6O on a Bruker Av 600 NMR instrument with TMS as the internal standard. HRESI-MS were recorded on a QSTAR XL LC MS MS applied bio systems spectrometer. Column chromatography was conducted using silica-gel (Kiesegel 60; 70-230 mesh), and, for TLC, silica-gel F254 aluminum sheets (0.25 mm thickness) were used. Compounds were detected Dragendorff’s reagent. Plant material: The roots and stem of Zizyphus oxyphylla Edgew were collected from Swat Valley (N.W.F.P, Pakistan) and identified by Dr. Hassan Sher, (taxonomist at Jahanzeb College, Swat, Pakistan). A voucher specimen (no. NH-012) has been deposited at National Herbarium Islamabad.
1208 Natural Product Communications Vol. 5 (8) 2010
Extraction and isolation: Air dried powdered roots of Zizyphus oxyphylla (8 kg) were macerated in methanol (3 x 7 days x 20 L). On removal of the solvent under vacuum at 35-40 oC, 372 g of crude extract was obtained, which was partitioned between water and dichloromethane. The dichloromethane extract (2.5 g) was subjected to CC using silica gel (300 mm x 20 mm) and hexanes/acetone/diethylamine (75:25:0.1, 10 L) to afford 8 fractions (A-H). Compounds 1 (10.2 mg) and 2 (8.7 mg) were obtained from fractions D (41.3 mg) and E (53.4 mg) by preparative TLC (hexanes/acetone/ diethyl amine, 15:10:1). Air dried stem powder (8 kg) was extracted in a similar manner to give 375 g of crude extract, which was partitioned between water and chloroform. The chloroform extract (11.0 g) was subjected to column chromatography over silica gel (325 mm x 65 mm) with hexanes/acetone/diethyl amine (75:25:0.1, 10 L) to afford 8 fractions (A-H). Fraction C (202 mg) was subjected to preparative TLC (hexanes/acetone/ diethylamine, 15:10:1) to obtain compound 3 (6.1 mg). (3S,7R,13S)-6-[2-(Dimethylamino)-3-phenylpropanoyl] -19-methoxy-2-oxa-6,9,15-triazatetracyclo[16.3.1.03,7.09,13] docosa-1-(22),16,18,20-tetraene-8,14-dione (1) [α]D25: -82.6 (c 0.02, acetone) IR (KBr): 3396 (NH), 1643 and 1697 (amide), 1508 (C=C) cm-1. UV λmax (MeOH): 319 and 264 nm.
Nisar et al.
H and 13C NMR (acetone-d6): Table 1. HRESI-MS: m/z 533.2323 (calcd. for C30H36N4O5 +H = 533.1763) EI-MS m/z (%): 148.0 (100), 91 (7.0), 84 (17) 1
Nummularin-C (2) [α]D25: -370.0 (c 0.2, acetone) IR (KBr): 3310 (NH), 1625 and 1670 (amide), 1508 (C=C) cm-1. UV λmax (MeOH): 319 and 265 nm. 1 H and 13C NMR (acetone-d6): Table 1. HRESI-MS: m/z 549.2664 (calcd. for C31H40N4O5 +H = 549.3076) EI-MS m/z (%): 457 (8.0), 148.0 (100), 84 (7) Nummularine-R (3) [α]D25: -72.4 (c 0.03, acetone) IR (KBr): 3383, 3248 (NH), 1670 (amide), 1625 (C=C) cm-1. UV λmax (MeOH): 322 and 266 nm. 1 H and 13C NMR (acetone-d6): Table 1. HRESI-MS: m/z 588.2789 (calcd. for C33H41N5O5 +H = 588.3185) EI-MS m/z (%): 457 (47), 187.0 (92), 84 (100) Acknowledgment - The authors are thankful to HEC (Higher Education Commission, Pakistan) for financial support and Dr. Hassan Sher (taxonomist at Jahanzeb College, Swat, Pakistan).
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Natural Product Communications 2010 Volume 5, Number 8 Contents Original Paper
Page
Phytochemical Investigation of Verbesina turbacensis Kunth: Trypanosome Cysteine Protease Inhibition by (–)-Bornyl Esters Ifedayo V. Ogungbe, Rebecca A. Crouch, William A. Haber and William N. Setzer
1161
Anti-herpetic Activities of Chemical Components from the Brazilian Red Alga Plocamium brasiliense Wilton José Ferreira, Rodrigo Amaro, Diana Negrão Cavalcanti, Claudia Moraes de Rezende, Viveca Antonia Giongo Galvão da Silva, Juliana Eymara Barbosa, Izabel Christina Nunes de Palmer Paixão and Valéria Laneuville Teixeira
1167
Chemical Constituents of the Soft Coral Sarcophyton infundibuliforme from the South China Sea Xue-Ping Sun, Chang-Yun Wang, Chang-Lun Shao, Liang Li, Xiu-Bao Li, Min Chen and Pei-Yuan Qian
1171
Metabolites from the Fungus Phoma sp. 7210, Associated with Aizoon canariense Jingqiu Dai, Hidayat Hussain, Siegfried Dräger, Barbara Schulz, Tibor Kurtán, Gennaro Pescitelli, Ulrich Flörke and Karsten Krohn
1175
Triterpenes from Protium hebetatum Resin Delcio Dias Marques, Ilmar Bernardo Graebner, Telma Leda Gomes de Lemos, Luciana Lucas Machado, Jõao Carlos Costa Assunção and Francisco José Queiroz Monte
1181
Cytotoxicity of 9,11-Dehydroergosterol Peroxide Isolated from Ganoderma lucidum and its Target-related Proteins Ya-Jun Cui, Shu-Hong Guan, Li-Xing Feng, Xiao-Yi Song, Chao Ma, Chun-Ru Cheng, Wen-Bo Wang, Wan-Ying Wu, Qing-Xi Yue, Xuan Liu and De-An Guo
1183
Polar Alkaloids from the Caribbean Marine Sponge Niphates digitalis Erik L. Regalado, Judith Mendiola, Abilio Laguna, Clara Nogueiras and Olivier P. Thomas
1187
A Short Stereoselective Synthesis of Racemic 2-Epicalvine Basem A. Moosa and Shaikh A. Ali
1191
Cytochrome P450 3A4 Inhibitory Activity Studies within the Lycorine series of Alkaloids James McNulty, Jerald J. Nair, Mohini Singh, Denis J. Crankshaw, Alison C. Holloway and Jaume Bastida
1195
Analysis of Amaryllidaceae Alkaloids from Zephyranthes robusta by GC-MS and Their Cholinesterase Activity Lucie Cahlíková, Andrea Kulhánková, Klára Urbanová, Irena Valterová, Kateřina Macáková and Jiří Kuneš
1201
Stereochemistry and NMR Data Assignment of Cyclopeptide Alkaloids from Zizyphus oxyphylla Muhammad Nisar, Waqar Ahmad Kaleem, Achyut Adhikari, Zulfiqar Ali, Nusrat Hussain, Inamullah Khan, Mughal Qayum and M. Iqbal Choudhary
1205
Geranylated Flavonols from Macaranga rhizinoides Mulyadi Tanjung, Didin Mujahidin, Euis H. Hakim, Ahmad Darmawan and Yana M. Syah
1209
A New Biflavonyloxymethane from Pongamia pinnata Anindita Ghosh, Suvra Mandal, Avijit Banerji and Julie Banerji
1213
Anti-inflammatory and Gastroprotective Properties of Hypericum richeri Oil Extracts Gordana Zdunić, Dejan Gođevac, Marina Milenković, Katarina Šavikin, Nebojša Menković and Silvana Petrović
1215
Production of Flavonoids in Organogenic Cultures of Alpinia zerumbet Cristiane P. Victório, Rosani do Carmo de O. Arruda, Celso Luiz S. Lage and Ricardo M. Kuster
1219
Phenolic Compounds in Leaves of Alchornea triplinervia: Anatomical Localization, Mutagenicity, and Antibacterial Activity Tamara R. Calvo, Diego Demarco, Fabio V. Santos, Helen P. Moraes, Taís M. Bauab, Eliana A. Varanda, Ilce M. S. Cólus and Wagner Vilegas
1225
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