Mechanistic aspects of rearrangement of 16α-hydroxy-17-keto steroids to the 17β-hydroxy-16-keto isomers

Steroids

Volumn 73, Issue 8, 2008, Pages 798-805

  Numazawa, Mitsuteru ^a   Nagaoka, Masao ^a   Matsuzaki, Hisao ^a   Yamashita, Kouwa ^a   Komatsu, Sachiko ^a   Osawa, Yoshio ^b  

^a TOHOKU PHARMACEUTICAL UNIVERSITY   (Japan)

^b HAUPTMAN WOODWARD MEDICAL RESEARCH INSTITUTE   (United States)

Author keywords

16 Hydroxy 17 keto steroid; 17 Hydroxy 16 keto steroid; Basic condition; Computational calculation; Ketol rearrangement; Mechanism

Indexed keywords

CYCLOHEXANE; CYCLOPENTANE; DEUTERIUM; KETOL; OXYGEN 18; STEROID;

ARTICLE; HYDRATION; ISOMER; REACTION ANALYSIS;

ACETYLATION; ISOMERISM; MAGNETIC RESONANCE SPECTROSCOPY; MASS SPECTROMETRY; STEROIDS;

EID: 44249124463     PISSN: 0039128X     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.steroids.2008.03.001     Document Type: Article

References (31)

1. 5-androstenetriol-3β,16,17. J Biol Chem 150 (1943) 363-379
2. 5-androstene-3β,16,17-triol from the urine of normal human males and females. Biochem J 38 (1944) 322-324
3. Fotherby K., Colas A., Atherden S., and Marrian G. The isolation of 16α-hydroxy-dehydroepi-androsterone (3β: 16α-dihydroxyandrost-5-en-17-one) from the urine of normal men. Biochem J 66 (1957) 664-669
4. Raju U., Bradlow H.L., Skidmore F.D., and Levitz M. The concentration of 16α-hydroxy-androgens in serum and cyst fluid of women with gross cystic disease of the breast. Steroids 54 (1989) 101-112
5. Starka L., and Hampl L. Minireview: 16α-hydroxylated metabolites of dehydroepi-androsterone and their biological significance. Endocr Regul 34 (2000) 161-165
6. Heřt J., Hill M., and Hampl R. Gas chromatographic-mass spectrometric identification of 16α-hydroxy-dehydroepiandrosterone in human seminal plasma. Steriods 69 (2004) 773-777
7. Adlercreutz H., Tikkanen M.J., and Hunneman D.H. Mass fragmentographic determination of eleven estrogens in the body fluids of pregnant and nonpregnant subjects. J Steroid Biochem 5 (1974) 211-217
8. Ikegawa S., Lahita R., and Fishman J. Concentration of 16α-hydroxyestrone in human plasma as measured by a specific RIA. J Steroid Biochem 18 (1983) 329-332
9. Adlercreutz H., Fotsis T., Bannwart C., Hämäläinen E., Bloigu S., and Ollus A. Urinary estrogen profile determination in young Finnish vegetarian and omnivorous women. J Steroid Biochem 24 (1986) 289-296
10. Xu X., Duncan A.M., Merz-Demlow B.E., Phipps W.R., and Kurzer M.S. Menstrual cycle effects on urinary estrogen metabolites. J Clin Endocrinol Metab 84 (1999) 3914-3918
11. Adlercreuz H., and Martin F. Oestrogens in human pregnancy faces. Acta Endocrinol 83 (1976) 410-419
12. Lønming P.E., Skulstad P., Sunde A., and Thorsen T. Separation of urinary metabolites of radiolabelled estrogens in man by HPLC. J Steroid Biochem 32 (1989) 91-97
13. Hobkirk R., and Nilsen M. Six estrogen fractions in human pregnancy urine. Acta Endocrinol Suppl. 51 (1960) 1111
14. Magendantz H., and Ryan K. Isolation of an estriol precursor, 16α-hydroxydehydroepi-androstetone, from human umbilical sera. J Clin Endocrinol 24 (1964) 1155-1162
15. Colás A., Heinrichs W., and Tatum H. Pettenkofer chromogens in the maternal and fetal circulations: detection of 3β,16α-dihydroxy-androst-5-en-17-one in umbilical cord blood. Steroids 3 (1964) 417-434
16. 19 steroids; their significance and factors related to their biosynthesis. In: Hobkirk R. (Ed). Steroid biochemistry (1979), CRC Press, London, England 133-179
17. Lardy H. A postulated rote for 16α-hydroxydehydroepiandrosterone in the prevention of respiratory distress syndrome. Med Hypotheses 66 (2006) 107-109
18. Bucala R., Fishman J., and Cerami A. Formation of covalent adducts between cortisol and 16α-hydroxyestrone and protein: possible role in the pathogenesis of cortisol toxicity and systemic lupus erythematosus. Proc Natl Acad Sci USA 79 (1982) 3320-3324
19. Fishman J., Schneider J., Hershcopf R.J., and Bradlow H.L. Increased estrogen-16α-hydroxylase activity in women with breast cancer and endometrial cancer. J Steroid Biochem 20 (1984) 1077-1081
20. Osborne M.P., Bradlow H.L., Wong G.Y.C., and Telang N.T. Upregulation of estradiol C16α-hydroxylation in human breast tissue: a potential biomarker of breast cancer risk. J Natl Cancer Inst 85 (1993) 1917-1920
21. Johnson W.S., Gastambide B., and Pappo R. The action of lead tetraacetate on an enol acetate. The epimeric 16-acetoxy derivatives of epiandrosterone acetate, their interconversion and rearrangement. J Am Chem Soc 79 (1957) 1991-1994
22. Fishman J. Rearrangements of steroidal ring D ketols. J Am Chem Soc 82 (1960) 6143-6147
23. Bernstein S., and Cantrall E.W. 16-Hydroxylated steroids. XVIII. 16-Hydroxylated 19-nor-androgens. J Org Chem 26 (1961) 3560-3563
24. Kirk D.N., and Hartshorn M.P. Ketal rearrangement. Steroid reaction mechanisms (1968), Elsevier Publishing Co., Amsterdam, The Netherland pp. 388-90
25. Numazawa M., and Osawa Y. Controlled alkaline hydrolysis of 16-bromo-17-keto steroids without ketol rearrangement and its reaction mechanism. J Am Chem Soc 102 (1980) 5402-5408
26. Numazawa M., Nagaoka M., and Osawa Y. Stereospecific synthesis of 16α-hydroxy-17-oxo steroids by controlled alkaline hydrolysis of corresponding 16-bromo-17-ketones and its reaction mechanism. J Org Chem 47 (1982) 4024-4029
27. Numazawa M., and Nagaoka M. Intramolecular 1,2-hydride shift in the rearrangement of steroidal 16β-hydroxy-17-ones to 17β-hydroxy-16-ones. J Chem Soc Chem Commun (1982) 530-531
28. Numazawa M., Nagaoka M., and Mutsumi A. Stereospecific 1,2-hydride shift in the rearrangement of 16β-hydroxy-17-oxo steroids to 17β-hydroxy-16-ones with acid and base. Chem Pharm Bull 35 (1987) 4763-4768
29. Catsoulacos P., and Hassner A. Conversion of steroidal α-bromo ketones to ketol by means of hydrazine. J Org Chem 32 (1967) 3723-3724
30. Kincl F.A. An improved synthesis of 16β-hydroxy dehydroepiandrosterone. J Steroid Biochem 7 (1976) 419-420
31. Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., et al. Gaussian 03, Revision D. 01 (2004), Gaussian Inc., Wallingford, CT