Summary
On the basis of comparative spectral data, the structures of 3 novel steroidal glycosides from the Mediterranean starfishHacelia attenuata have been elucidated as3, 4 and5. These are further examples of a novel group of 24-O-glycosidated steroids recently encountered in the same species and in the Pacific speciesProtoreaster nodosus.
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Riccio, R., Minale, L., Pizza, C., Zollo, F., and Pusset, J., Tetrahedron Lett.23 (1982) 2899.
Eggert, H., Van Antwerp, C.L., Bhacca, N.S., and Djerassi, C., J. org. Chem.41 (1976) 71.
Van Antwerp, C.L., Eggert, H., Meakins, C.D., Miners, J.O., and Djerassi, C., J. org. Chem.42 (1977) 789.
The heptaacetate3a was prepared by using an excess of acetic anhydride in pyridine at room temperature,1H NMR (270 MHz, CDCl3), δ 0.86 (d, J=6.7 Hz, 26- and 27-H), 0.93 (d, J=7.0 Hz, 21-H), 1.22 (s, 19-H), 1.29 (s, 18-H), 2.03, 2.09 and 2.10 (singlets, 21H, CH3C=O), 3.31 (m, overlapping with 5″-Hax, 24-H), 3.92 (bs, W1/2=7 Hz, 4α-H), 4.66 (dt, J=11.0 and 4.2 Hz, 3α-H), 5.12 (m, overlapping with 3″-H, 15α-H), 5.40 (ddd, J=10.5, 10.5 and 3 Hz, 6β-H).
3b,1H NMR (270 MHz, CDCl3), δ 0.86 (d, J=6.7 Hz, 26- and 27-H), 0.93 (d, J=7.0 Hz, 21-H), 1.00 (s, 19-H), 1.21 (s, 18-H), 2.03, 2.10, 2.11, 2.14 (singlets, 21H, CH3C=O), 2,47 (d, J=10.5, H-5), 3.31 (m, overlapping with 5″-Hax, 24-H), 5.10–5.20 (m, overlapping with 3″-H and 5′-H, 3α-H and 15α-H), 5.52 (ddd, J=10.5, 10.5 and 3.0 Hz, 6β-H).
Liu, H.W., and Nakanishi, K., J. Am. chem. Soc.103 (1981) 559.
Ritchie, R.G.S., Gyr, N., Korsh, B., Koch, H.J., and Perlin, A.S., Can. J. Chem.53 (1975) 1424.
The monophenylboronates of3 and4 were characterized by1H NMR-spectroscopy:3, δ 1.11 (3H, s, 18-H), 1.48 (3H, s, 19-H), 4.27 (1H, ddd, J=10.5, 10.5, 4.0 Hz, 6β-H), 4.68 (1H, brt, J=5.5 Hz, 15α-H); the remaining hydroxymethine signals as well as the sugar signals remained essentially unshifted; aromatics: δ 7.35 (3H, m), 7.75 (2H, d, J=7.5 Hz);4, δ 1.11 (3H, s, 18-H), 1.48 (3H, s, 19-H), 4.27 (1H, ddd, J=10.5, 10.5, 4.0 Hz, 6β-H), 4.68 (1H, brt, J=5.5 Hz, 15α-H); the remaining hydroxymethine signals as well as the sugar signals remained essentially unshifted; aromatics: δ 7.35 (3H, m), 7.75 (2H, d, J=7.5 Hz).
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Part 9. L. Minale, C. Pizza, R. Riccio and F. Zollo, Experientia39 (1983) 567. This contribution is part of the Progetto Finalizzato ‘Chimica fine e secondaria’ del C.N.R., Roma.
Acknowledgments. We thank Prof. K. Nakanishi, Columbia University, New York, for FD-mass spectral analyses, the Centro Interfacoltà di Metodologie Chimico-Fisiche for 270 MHz NMR facilities, and Miss R. Aquino for part of the experimental work.
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Minale, L., Pizza, C., Riccio, R. et al. Starfish saponins. Part 101. Further 24-O-glycosidated steroids from the starfishHacelia attenuata. Experientia 39, 569–571 (1983). https://doi.org/10.1007/BF01971100
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DOI: https://doi.org/10.1007/BF01971100