A systematic NMR approach for the determination of the molecular structure of steroidal saponins

Advances in Experimental Medicine and Biology

Volumn 405, Issue , 1996, Pages 299-315

  Agrawal, Pawan K ^a  

^a CSIR CENTRAL INSTITUTE OF MEDICINAL AND AROMATIC PLANTS   (India)

Author keywords

[No Author keywords available]

Indexed keywords

CHOLESTANE DERIVATIVE; SAPOGENIN; SAPONIN DERIVATIVE; SPIROSTAN DERIVATIVE; STEROID;

CHEMICAL BINDING; CHEMICAL STRUCTURE; CONFERENCE PAPER; CYCLIZATION; NUCLEAR MAGNETIC RESONANCE; NUCLEAR OVERHAUSER EFFECT; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0029823735     PISSN: 00652598     EISSN: None     Source Type: Book Series    
DOI: 10.1007/978-1-4613-0413-5_26     Document Type: Conference Paper

References (117)

1. R. Hardman, Recent developments in our knowledge of steroids. Planta Med., 53:233 (1987).
2. S.B. Mahato, A.N. Ganguli and N.P. Sahu, Steroidal saponins, Photochemistry, 21:639 (1987).
3. G. Voigt and K. Hiller, Neuere Ergebnisse zur Chemie und Biologie der Steroid Saponine, Sci. Pharm. 55:201 (1987).
4. A. Martson and K. Hostettmann, Plant molluscicides, Phytochemistry, 24:639 (1985).
5. R. Tschesche and G. Wulff, Chemie und Biologie der Saponins, in Fortschritte der Chemie Organische Naturstoffe, W. Herz, H. Grisebach and G.W. Kirby, Eds, Springer Verlag, Berlin, 30:461 (1973).
6. S.D. Kravets, Yu.S. Vollemer, M.B. Gorovits and N.K. Abubikarov, Steroids of spirostan and furostan series from plants of the genus Allium, Khim. Prir. Soed., 429 (1990).
7. E. Heftmann, Biogenesis of steroids in Solanaceae, Phytochemistry, 22:1843 (1983).
8. 2] acetate in Dioscorea tokoro tissue culture, J. Chem. Soc., Perkin Trans I, 869 (1984).
9. 1H NMR and HPLC resolution of (25R)- and (25S)-26-hydroxycholesterol, J. Chem. Soc., Perkm Trans I, 1713 (1987).
10. A.V. Patel, G. Blunden, T. Crabb, Y. Sauvaire and Y. Baccou, A. review of naturally occurring steroidal sapogenins, Fitoterapia, 58:56 (1987).
11. 13C NMR of steroids, Org. Magn. Reson., 9:439 (1977).
12. D.H. William and I. Flemming, Spectroscopic Methods in Organic Chemistry, 4th edn., McGraw Hill, London (1987).
13. P.K. Agrawal, S.K. Srivastava and W. Gaffield, Carbon-13 NMR spectroscopy of steroidal alkaloids, in Alkaloids: Chemical and Biological Perspectives, S.W. Pelletier Ed., Springer Verlag, New York, Vol 7, pp.49 (1991).
14. P.K. Agrawal, D.C. Jain, R.K. Gupta and R.S. Thakur, Carbon-13 NMR steroidal sapogenins and steroidal saponins, Phytochemistry, 24:2479 (1985).
15. P.K. Agrawal, D.C. Jain and A.K. Pathak, NMR spectroscopy of steroidal sapogenins and steroidal saponins: an update, Magn. Reson. Chem., in press.
16. S.L. Patt and J.N. Shoolery, Attached proton test for carbon-13 NMR. J. Magn. Reson., 46:435 (1982).
17. D.M. Doddrell, D.T. Pegg and M.R. Bendall, Distortionless enhancement of NMR signals by polarization transfer, J. Magn. Reson., 48:323 (1982).
18. 15N NMR: polarization transfer using the INEPT pulse sequence, J. Am. Chem. Soc., 102:428 (1980).
19. 13C coupling observed via double-quantum coherence, J. Am. Chem. Soc., 102:4849 (1980).
20. This experiment was first proposed by Jeener (J. Jeener, Ampere International Summer School II, Basko Polje), Yugoslavia, (1971).
21. W.P. Aue, J. Karhan and R.R. Ernst, Homonuclear broad band decoupling and two-dimensional J-resolved NMR spectroscopy, J. Chem. Phys., 64:4226 (1976).
22. A. Bax and R. Freeman, Investigation of complex networks of spin-spin coupling by two-dimensional NMR. J. Magn. Reson., 44:542 (1981).
23. 1H NMR spectra of proteins via double-quantum filtering. Biochem. Biophys. Res. Commun., 17:479 (1983).
24. C. Griesinger, O.W. Sorensen and R.R. Ernst, Two-dimensional correlation of connected NMR transitions. J. Am. Chem. Soc., 107:6394 (1985).
25. T. Domke, P. Xu and R, Freeman, Geminal filtered correlation spectroscopy, J. Magn. Reson., 92:218 (1991).
26. 1H NMR spectra by selective excitation of experimental subspectra, J. Am. Chem. Soc., 104:6800 (1982).
27. G. Wagner, Two-dimensional relayed coherence transfer spectroscopy, J. Magn. Reson., 55:151 (1983).
28. S.W. Homans, R.A. Dwek, D.L. Fernandes and T.W. Rademacher, Multi-step relayed correlation spectroscopy: sequential resonance assignments in oligosaccharides, Proc. Natl. Acad. Sci. U.S.A., 81:6286 (1984).
29. 1H NMR spectra via two-dimensional homonuclear Hartmann-Hahn spectroscopy, J. Am. Chem. Soc., 107:2820 (1985).
30. A. Kumar, R.R. Ernst and K. Wuthrich, A two-dimensional nuclear Overhauser enhancement (2D NOE) experiment for the evolution of complete proton-proton cross relaxation networks in biological molecules, Biochem. Biophys. Res. Commun., 95:1 (1980).
31. A.A. Bothner-By, R.L. Stephens, J.T. Lee, C.D. Warren and R.W. Jeanloz, Structure determination of a tetrasaccharide by transient nuclear Overhauser effects in the rotating frame, J. Am. Chem. Soc., 106:811 (1984).
32. G. Bodenhausen and R. Freeman, Correlation of protonated carbon-13 NMR spectra by heteronuclear two-dimensional spectroscopy, J. Magn. Reson., 28:471 (1977).
33. A. Bax, W. Egan and P. Kovac, New NMR techniques for structure determination and resonance assignments of complex carbohydrates, J. Carbohydr. Chem., 3:593 (1984).
34. A. Bax and S. Subramanian, Sensitivity-enhanced two-dimensional heteronuclear shift correlation NMR spectroscopy, J. Magn. Reson., 67:565 (1986).
35. G.E. Martin and A.S. Zektzer, Long-range two-dimensional heteronuclear shift correlation, Magn. Reson. Chem., 26:631 (1988).
36. 13C assignments from sensitivity enhanced detection of heteronuclear multiple-bond connectivity by 2D multiple-quantum NMR, J. Am. Chem. Soc., 108:2093 (1986).
37. W.R. Croasmum and R.M.K. Carlson, Steroid structural analysis by two-dimensional NMR, In Two-Dimensional NMR spectroscopy, Application for Chemists and Biochemists, Verlag Chemie, New York, pp 387 (1987).
38. G.A. Morris, Modern NMR techniques for structure elucidation, Magn. Reson. Chem., 24:371 (1986).
39. A.E. Derome, Modern NMR Techniques for Chemical Research, Pergamon Press, New York (1987).
40. J.K.M. Sanders and B.K. Hunter, Modern NMR Spectroscopy: A Guide for Chemists, Oxford University Press, Oxford (1987).
41. J. Keeler, Two-dimensional nuclear magnetic resonance spectroscopy, Chem. Soc. Rev., 19:381 (1990).
42. P.K. Agrawal, Two-dimensional NMR spectroscopy in the structure determination of natural products. J. Sci. Indust. Res., 53:329 (1994).
43. A.E. Derome, The use of NMR spectroscopy in the structure determination of natural products: two-dimensional methods, Nat. Prod Rep., 6:111 (1989).
44. 13C and proton NMR, J. Nat. Prod. 47:226 (1984).
45. I.H. Sadler, The use of NMR spectroscopy in the structure determination of natural products: one-dimensional methods, Nat. Prod. Rep., 5:101 (1988).
46. W.S. Brey, Ed., Pulse Methods in 1D and 20 Liquid-phase NMR, Academic Press, San Diego (1988).
47. R.R. Ernst, G. Bodenhausen and A. Wokun, Principles of Nuclear Magnetic Resonance in One and Two Dimensions, Oxford University Press, Oxford (1987).
48. P.K. Agrawal, C.A. Bush, N. Qureshi and K. Takayama, Structural analysis of lipid A and re-lipopolysaccharides by NMR spectroscopic methods, Adv. Biophys. Chem., 4:179 (1994).
49. S. Kubo, Y. Mimaki, Y. Sashida, T. Nikiado and T. Ohmoto, Steroidal saponins from the rhizomes of Smilax sieboldii, Phytochemistry, 31:2445 (1992).
50. T. Morita, T. Ushiroguchi, N. Hayashi, H. Matsuura, Y. Itakura and T. Fuwa, Steroidal saponins from elephant garlic, bulbs of Allium ampeloprasum L., Chem. Pharm. Bull., 36:675 (1993).
51. Y. Mimaki, Y. Sashida, O. Nakamura, T. Nikiado and T. Ohmoto, Steroidal saponin from the bulbs of Lilium regal and L. henryi. Phytochemistry, 33:675 (1993).
52. X.C. Li, C.R. Yang, M. Ichikawa, H. Matsuura, R. Kasai and K. Yamasaki, Steroidal saponins from Polygonatum kingianum, Phytochemistry, 31:3559 (1992).
53. Yu. S. Vollerner, S.D. Kravets, A.S. Sashkov, B. Tashkhodzhaev, M.B. Gorovits, M.R. Yagudaev and N.K. Abubikarov, Alliosterol and alliosides A and B from Allium suvorovii and Allium stipitatum - Structural analog of furostanols. Khim. Prir. Soed., 231 (1991).
54. M.H. Yang, G. Blunden, A. Patel, T.A. Crabb, K. Brain and W.J. Griffin, Two furostane saponins from Cordyline rubra. Phytochemistry, 29:1332 (1990).
55. H. Shimomura, Y. Sashida and Y. Mimaki, 26-O-acylated furostanol saponins pardarinoside A and B from bulbs of Lilium pardarinum, Chem. Pharm. Bull., 36:3226 (1988).
56. J. Kim, J.M. Pezzuto, D.D. Soejarto, F.A. Lang and A.D. Kinghorn, Polypodoside A, an intensely sweet constituent of the rhizomes of Polypodium glycyrrhiza, J. Nat. Prod., 51:1166 (1988).
57. M. Nishizawa, H. Yamada, Y. Yamaguchi and S. Hatakeyama, Structure revision of polypodoside A: major sweet principle of Polypodium glycyrrhiza, Chem. Lett., 1555 (1994).
58. H. Shimomura, Y. Sashida, Y. Mimaki and Y. Iitaka, Studies on the constituents of Lilium henryi B, Chem. Pharm. Bull., 36:2430 (1988).
59. S. Okamura, K. Shingu, S. Yahara, H. Kohda and T. Nohara, Two Steroidal glycosides from Scopolia japonica, Chem. Pharm. Bull., 40:2981 (1992).
60. Y. Ju and Z. Jia, Steroidal saponins from the rhizomes of Smilax menispermoidea, Phytochemistry, 31:1349 (1992).
61. W. Willker and D. Liebfritz, Complete assignment and conformational analysis of tomatine and tomatidine, Magn. Reson. Chem., 30:645 (1992).
62. A.K. Pathak, P.K. Agrawal, D.C. Jain, R.P. Sharma and O.W. Howarh, NMR studies of 20β-hydroxyecdysone, a steroid isolated from Tinospora cordifolia, Indian J. Chem., 346:674 (1995).
63. 13C assignments by two-dimensional NMR spectroscopy, Magn. Reson. Chem., 31:278 (1993).
64. 1H coupling interactions: Identification of different pathways by 2D NMR δ-δ correlated spectroscopy. Application in structural analysis, Magn. Reson. Chem., 25:311 (1987).
65. H. Schroder and E. Haslinger, Long-range proton spin-spin coupling in rigid cyclic structures by 2D NMR through space coupling. Magn. Reson. Chem., 32:12 (1994).
66. 1H homonuclear shift correlated nuclear magnetic resonance spectroscopy (COSYDEC) applied to steroids. Steroids, 56:195 (1991).
67. 1H NMR spectra of the steroid hormones, their hydroxylated derivatives, and related compounds, J. Chem. Soc., Perkin Trans. II, 1567 (1990).
68. 13C NMR assignments for a stereoisomeric pair of steroidal sapogenins: smilagenin and sarsasapogenin, Manuscript in preparation.
69. J. Peng, X. Yao, H. Kobayashi and C. Ma, Macrostemonosides, novel furostanol glycosides from Allium macrostemon, Planta Med., 61:58 (1995).
70. J.T. Branke and E. Haslinger, Spirostanol glycoside from the tuber Ophiopogon japonicus, Liebigs Ann. Chem., 537 (1995).
71. Y. Takashi, Y. Mimaki, A. Kameyama, Y. Sashida, T. Nikaido and T. Ohmoto, Recurvosides A-E, new polyhydroxylated steroidal saponins from Nolina recurvata stems, Tetrahedron. 51:2281 91995)
72. T. Horikawa, Y. Mimaki, Y. Sashida, T. Nikaido and T. Ohmoto, Aculeoside A, a novel steroidal saponin containing a deoxyaldoketose from Ruscus aculeatus, Chem. Lett., 2303 (1994)
73. T. Inoue, Y. Mimaki, Y. Sashida, T. Nikaido and T. Ohmoto, Steroidal saponins from the tubers of Dechelostemma multiflorum and their inhibitory activity on cyclic -AMP phosphodiesterase. Phytochemistry, 39:1103 (1995).
74. T. Faecke and S. Berger, Complete proton assignment in acetylcholesterol using ge-SELINCOR-TOCSY, Tetrahedron, 51:3521 (1995).
75. T. Faecke and S. Berger, SERF, a new method for H, H spin coupling measurement in organic chemistry, J. Mag. Reson., Ser. A. 113:114 (1995).
76. G. Pant, M.S. Panwar, D.S. Negi, M.S.M. Rawat, G.A. Morris and R.I.G. Thompsen, Structure elucidation of a spirostanol glycoside from Aspergus officinalis fruits by concerted use of two-dimensional NMR techniques, Magn. Reson. Chem., 26:911 (1988).
77. T. Yamashita, T. Matsumoto, S. Yahara, N. Yoshida and T. Nohara, Structures of two new steroidal glycosides, soladulcosides A and B from Solanum dulcamara, Chem. Pharm. Bull., 39:1626 (1991).
78. Y. Mimaki, N. Ishibashi, K. Ori and Y. Sashida, Steroidal glycosides from the bulbs of Lilium dauricum, Phytochemistry, 31:1753 (1992).
79. 13C NMR spectroscopy of oleanane triterpenoids, Progr. NMR Spectrosc., 24:1 (1992)
80. V. Dirsch, M. Lacaille-Dubois and H. Wagner, Dracoside, a new steroidal saponin from Helleboru purpurascens, Nat. Prod. Lett., 4:29 (1994).
81. G. Blunden, A.V. Patel and T.A. Crabb, Microbiological transformations of hecogenin and diosgenin by Cunninghamella elegans, Phytochemistry, 29:1771 (1990).
82. 13C NMR spectroscopy of (25R)-5α-spirostanes, Magn. Reson. Chem., 25:831 (1987).
83. O. Nakamura, Y. Mimaki, Y. Sashida, T. Nikaido and T. Ohmoto, Agapanthussaponins A-D, new potent cAMP phosphodiesterase inhibitors from the underground parts of Agapenthus inapertus, Chem. Pharm. Bull., 41:1784 (1993).
84. K. Nakano, K. Murakami, Y. Takaishi, T. Tomimatsu and T. Nohara, Studies on the constituents of Haloniopsis orientalis (Thunb) c. Tanaka, Chem. Pharm. Bull., 37:116 (1989).
85. Y. Renzhou, W. Dezu and F. Jian, Carbon-13 NMR spectra of ten steroidal sapogenins, Acta. Bot. Yunnan., 9:374 (1987).
86. T. Konishi, S. Kiyosawa and J. Shoji, Studies on the coloration mechanism of furostanol derivatives with Ehrlich reagent. I. On the reaction of 3,26-dimethoxyfurosta-5,20-diene with Ehrlich reagent. Chem. Pharm. Bull., 32:2111 (1987).
87. K. Nakano, T. Nohara, T. Tomimatsu and T. Kawasaki, 18-Norspirostanol derivatives from Trillium tschonoskii, Phytochemistry, 22:1047 (1983).
88. Y. Sashida, K. Kawashima and Y. Mimaki, Novel polyhydroxylated steroidal saponins from Allium giganteum, Chem. Pharm. Bull., 39:698 (1991).
89. 13C NMR spectroscopy. The INADEQUATE pulse sequence, Angew. Chem. Int. Ed. Engl., 26:625 (1987).
90. K. Kudo, K. Miyahara, N. Marubayashi and T. Kawasaki, Characterization of a minor compound which accompanies the usual 22α(R)-O,25β(S)-spirostanol glycoside, as a novel type of 22β(S)-O-25α(S)analog. Chem. Pharm. Bull., 32:4229 (1984).
91. 13C NMR spectroscopy, Phytochemisrty, 28:1985 (1989).
92. M. Ono, K. Shoyama and T. Nohara, The constituents of Chinese Polygonati officinalis rhizome and Poligonati rhizoma, Shoyakugaku Zasshi, 42:135 (1988).
93. A.M.E. Abdel-Aziz, K. R. Brain, G. Blunden, T. Crabb and A.K. Bashir, Steroidal saponins from Tacca leontopetaloides, Planta Med., 56:218 (1990).
94. A. Abdel-Aziz, K. Brain, G. Blunden, T. Crabb and A.K. Bashir, Isomeric F-ring dihydroxylated 22,25-epoxyfurostane an spirostane sapogenins from Tacca leontopetaloides, Phytochemistry, 29:1643 (1990).
95. K. Bock, C. Pedersen and H. Pedersen, Carbon-13 NMR data for oligosaccharides, Adv. Carbohydr. Chem. Biochem., 42:193 (1984).
96. P.K. Agrawal, NMR spectroscopy in the structural elucidation of oligosaccharides and glycosides, Phytochemistry, 31:3307 (1992).
97. J. Dabrowski, Two-dimensional proton magnetic resonances spectroscopy, Meth. Enzymol., 179:122 (1989).
98. C.A. Bush, High resolution NMR in the determination of the structure of complex carbohydrates. Bull. Magn. Reson., 10:73 (1989).
99. S.W. Romans, Oligosaccharide conformations: application of NMR and energy calculations. Progr. NMR Spectrosc.,22:55(1990).
100. 13C NMR assignments of 2,3-diacetylamido-2,3-dideoxy-D-glucopyranose. J. Carbohydr. Chem., 11:945 (1992).
101. H. Schroeder, M. Schubert-Zsilaveez, G. Reznicek, J. Cart, J. Jurenitisch and E. Haslinger, A triterpene saponin from Herniaria glabra, Phytochemistry, 34:1609 (1993).
102. R. Bazzo, C.J. Edge, R.A. Dwek and T.W. Rademacher, Extracting subspectra from overlapping regions DOUBLE TOCSY, J. Mag. Reson., 86:199 (1990).
103. F. Inagaki, I. Shimada, D. Kohda, A. Suzuki and A. Bax, Relayed HOHAHA, a useful method for extracting subspectra of individual components of sgar chains. J. Magn. Reson., 81:186 (1989).
104. P.K. Agrawal and M.C. Bansal, in Studies in Organic Chemistry, Vol 39 Carbon-13 NMR of Flavonoids, P.K. Agrawal Ed Elsevier, New York, pp. 283 (1989).
105. N.K. Kochetkov, Microbial polysaccharides: new approaches, Chem. Soc. Rev., 19:29 (1990).
106. S. Chen and J.K. Snyder, Diosgenin-bearing molluscidal saponins from Allium vineale: an NMR approach for the structural assignment of oligosaccharide units. J. Org. Chem., 54:3679 (1988).
107. V.U. Ahmad, E.T. Baqai, I. Fatima and R. Ahmad, A spirostanol glycoside from Cestrum nocturnum, Phytochemistry, 30:3057 (1991).
108. Y. Mimaki, O. Nakamura, Y. Sashida, T. Nikaido and T. Ohmoto, Steroidal saponins from the bulbs of Triteleva lacta and their inhibitory activity on cyclic AMP phosphodiesterase. Phytochemistry, 30:1279 (1995).
109. P.K. Agrawal and A.K. Pathak, NMR spectroscopic approaches for the determination of interglycosidic linkage and sequence in oligosaccharides, Phytochem. Anal., accepted
110. G. Pant, M.C. Purohit, G.A. Morris, A.G.W. Halstead and R.I.G. Thompson, Structure elucidation and proton and carbon-13 assignments of a pentasaccharide glycoside from Agave americana, Magn. Reson. Chem., 32:213 (1994).
111. G.M. Clore and A.M. Gronenbom, Applications of three- and four-dimensional heteronuclear NMR spectroscopy to protein structure determination, Progr. NMR Spectrosc., 23:108 (1991).
112. G.W. Vuister, P.D. Waard, R. Boelens, J.F.G. Vliegenthart and R. Kaptein, The use of 3D NMR in structural studies of oligosaccharides, J. Am. Chem. Soc., 111:772 (1989).
113. 13C two-dimensional and three-dimensional HMQC-NOE at natural abundance on complex carbohydrates, J. Am. Chem. Soc., 112:3232 (1990).
114. D. Uhrin, J.R. Brisson and D.R. Buundle, Pseudo-3D NMR spectroscopy: application to oligo- and polysaccharides, J. Biomol. NMR, 3:367 (1993).
115. H. Kessler, S. Mronga and G. Gemmecker, Mutidimensional NMR experiments using selective pulses. Magn. Reson. Chem., 29:527 (1991).
116. H. Schroeder and E. Haslinger, Sequential analysis of oligosaccharide structures in a few minutes, Angew. Chem. Int. Ed. Engl., 32:1349 (1993).
117. T.A. Carpenter, L.D. Colebrook, L.D. Hall and G.K. Pierens, Application of gradient-selective COSY and double-quantum filtered gradient-selective COSY experiments to carbohydrates: 2-deoxy-D-arabino-hexose (2-deoxy-D-glucose). Carbohydr. Res., 241:267 (1993).