A. Kanakubo et al. / Tetrahedron 57 32001) 8801±8805
8805
8C-30, 50), 118.3 8C-4a), 118.7 8d, J5.5 Hz, C-6), 122.6 8C-
10), 123.7 8C-3), 126.4 8C-5), 130.2 8C-20, 60), 153.3 8C-2),
156.9 8C-8a), 157.4 8C-40), 159.2 8d, J4.0 Hz, C-7), 175.1
8C-4). 31P NMR 8162 MHz, DMSO-d6) d 11.05 8s).
ture8s) of Daidzein sulfate8s) and Genistein sulfate8s) based
on the results of enzymic hydrolysis, are to be reexamined.
A new ultra-micro analytical method to determine either
phosphate8s) or sulfate8s) is awaited beside 13C, 31P NMR
spectroscopy.
HRMS 8FAB) calcd for C15H10O7P 333.0164 8M-H)2,
found 333.0185 8M-H)2.
References
1
3.2.3. Genistein 3. H NMR 8600 MHz, DMSO-d6) d 6.21
1. Perkin, A. G.; Newbury, F. G. J. Chem. Soc. 1899, 75, 830.
2. Steglich, E.; Fugmann, B.; Lang-F, S. Iso¯avones in Natural
Products; Georg Thieme Verlag: New York, 2000 p. 327.
3. Walter, E. D. J. Am. Chem. Soc. 1941, 63, 3273±3276.
4. 8a) Le, L. R.; Ahmadi, M.; Smith, H. J.; Nicholls, P. J.;
Whomsley, R. Pharm. Sci. 1996, 2, 21±23. 8b) Gamache,
P. H.; Acworth, I. N. Proc. Soc. Exp. Biol. Med. 1998, 217,
274±280. 8c) Nishihara, T.; Nishikawa, J.; Kanayama, T.;
Dakeyama, F.; Saito, K.; Imagawa, M.; Takatori, S.; Kitagawa,
Y.; Hori, S.; Utsumi, H. J. Health Sci. 2000, 46, 282±298.
5. Dohrman, A.; Miyata, S.; Gallup, M.; Li, J.-D.; Chapelin, C.;
Coste, A.; Escudier, E.; Nadel, J.; Carol, B. Biochim. Biophys.
Acta 1998, 1406, 251±259.
81H, d, J2.1 Hz, H-6), 6.37 81H, d, J2.1 Hz, H-8),6.81
82H, dbt, J8.4 Hz, H-30, -50), 7.36 82H, dbt, J8.4 Hz,
H-20, -60), 8.31 81H, s, H-2), 9.56p 81H, s, H-40), 10.86p
81H, s, H-7), 12.94 81H, s, H-5). 8p interchangeable).
13C NMR 8150 MHz) d 93.8 8C-8), 99.1 8C-6), 104.6 8C-4a),
115.2 8C-30, 50), 121.4 8C-10), 122.4 8C-3), 130.3 8C-20, 60),
154.1 8C-2), 157.6 8C-40), 157.7 8C-8a), 162.1 8C-5), 164.4
8C-7), 180.4 8C-4).
1
3.2.4. Genistein-7-O-phosphate 4. H NMR 8600 MHz,
DMSO-d6) d 6.59 81H, s, H-6), 6.80 82H, d, J8.4 Hz,
H-30, -50), 6.87 81H, s, H-8), 7.36 82H, d, J8.4 Hz, H-20,
-60), 8.34 81H, s, H-2).
6. 8a) Yasuda, T.; Kano, Y.; Ohsawa, K. Biol. Pharm. Bull. 1994,
17, 1369±1374. 8b) Yasuda, T.; Kano, Y.; Saito, K.; Ohsawa, K.
Biol. Pharm. Bull. 1995, 18, 300±303. 8c) Gamache, P. H.;
Acworth, I. N. Proc. Soc. Exp. Biol. Med. 1998, 217, 274±
280. 8d) Shelnutt, S. R.; Cimino, C. O.; Wiggins, P. A.; Badger,
T. M. Cancer Epidemiol., Biomarkers Prev. 2000, 9, 413±419.
7. Yasuda, T.; Mizunuma, S.; Kano, Y.; Saito, K.; Ohsawa, K.
Biol. Pharm. Bull. 1996, 19, 413±417.
13C NMR 8150 MHz) d 98.1 8d, J5.0 Hz, C-8), 103.0 8d,
J5.5 Hz, C-6), 105.7 8C-4a), 115.2 8C-30, 50), 121.3 8C-10),
122.4 8C-3), 130.2 8C-20, 60), 154.4 8C-2), 156.9 8C-8a),
157.6 8C-40), 161.1 8C-5), 161.3 8d, J4.5 Hz, C-7), 180.6
8C-4). 31P NMR 8162 MHz, DMSO-d6) d 11.27 8s).
HRMS 8FAB) calcd for C15H10O8P 349.0113 8M-H)2,
found 349.0146 8M-H)2.
8. 8a) Barnes, S.; Wang, C.-C.; Smith-J, M.; Kirk, M. J. Med. Food
1999, 2, 111±117. 8b) Coldham, N. G.; Howells, L. C.; Santi,
A.; Montesissa, C.; Langlais, C.; King, L. J.; Macpherson, D. D.;
Sauer, M. J. J. Steroid Biochem. Mol. Biol. 1999, 70, 169±184.
8c) Cimino, C. O.; Shelnutt, S. R.; Ronis, M. J. J.; Badger, T. M.
Clin. Chim. Acta 1999, 287, 69±82.
4. Summary
9. 8a) Pretsch, E.; Simon, W.; Seibl, J.; Clerc, J. In Tables of
Spectral Data for Structure Determination of Organic
Compounds, Fresenius, W., Huber, J. F. K., Pungor, E.,
Rechnitz, G. A., Simon, W., West, Th. S., Eds.; 2nd Ed.,
Springer: Berlin, 1989; p. C215. 8b) Silverstein, R. M.; Webster,
F. X. Spectrometric Identi®cation of Organic Compounds; 6th
Ed.; Wiley: New York, 1996 pp. 291±296.
We have concluded that the Daidzein and Genistein analogs
2 and 4 were deduced to be Daidzein-7-O-phosphate and
Genistein 7-O-phosphate, respectively. Although these
phosphates did indeed undergo hydrolysis with sulfatase
to give the corresponding iso¯avone molecules 1 and 3,
these facts do not give ®nal evidence of the presence of
sulfate group. Several papers that have reported the struc-