Synthesis of deuterium- and tritium-labeled 25,26,26,26,27,27,27-heptafluorocholesterol

Journal of Labelled Compounds and Radiopharmaceuticals

Volumn 42, Issue 6, 1999, Pages 509-518

  Su, Xiangdong ^a   Wilson, William K ^a   Schroepfer, George J ^a  

^a RICE UNIVERSITY   (United States)

Author keywords

Deuterium; NMR; Side chain fluorinated cholesterol; Tritium

Indexed keywords

DEUTERIUM; NUCLEAR MAGNETIC RESONANCE; TRITIUM;

CHEMICAL PURITY; ISOTOPE LABELING; LABELING STRATEGY; MAGNETIC RESONANCE SPECTRA; POTENTIAL VALUES; RADIOCHEMICAL PURITY; SIDE-CHAIN FLUORINATED CHOLESTEROL; SIDE-CHAINS; SPECIFIC ACTIVITY; SYNTHESISED;

CHOLESTEROL;

CARBON 13; CHOLESTEROL DERIVATIVE; DEUTERIUM; TRITIUM;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

TRITIUM;

EID: 0033058673     PISSN: 03624803     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1099-1344(199906)42:6<509::AID-JLCR211>3.0.CO;2-M     Document Type: Article

References (31)

1. (a) Javitt N.B. and Budai K. - Biochem. J. 262: 989-992 (1992).
2. (b) Taylor F.R., Saucier S.E., Shown E.P., Parish E.J., and Kandutsch A.A. - J. Biol. Chem. 259: 12382-12387 (1984).
3. (c) Pinkerton F.D., Pelley R.P., and Schroepfer G.J., Jr. - Biochem. Biophys. Res. Commun. 186: 569-572 (1992).
4. (d) Zhang J., Dricu A., and Sjövall J. - Biochim. Biophys. Acta 1344: 241-249 (1997).
5. (a) Kudo K., Emmons G.T., Casserley E.W., Via D.P., Smith L.C., Pyrek J.S., and Schroepfer G.J., Jr. - J. Lipid Res. 30: 1097-1111 (1989).
6. (b) Breuer O. and Björkhem I. - Steroids 55: 185-190 (1990).
7. (c) Dzeleiovic S., Breuer O., Lund E., and Diczfalusy U. - Anal. Biochem. 225: 73,80 (1995).
8. (d) Babiker A. and Diczfalusy U. - Biochim. Biophys. Acta 1392: 333-339 (1998).
9. a) Van Lier J.E. and Smith L.L. - Biochemistry 6: 3269-3278 (1967).
10. (b) Brooks C.J.W., Steel G., Gilbert J.D., and Harland W.A. - Atherosclerosis 13: 223-227 (1971).
11. (c) Brown A.J., Leong S.-L., Dean R.T., and Jessup W. - J. Lipid Res. 38: 1730-1745 (1997).
12. (d) Fumagalli R., Galli G., and Urna G. - Life Sci. 10: 25-33 (1971).
13. (e) Smith L.L. and Van Lier J.E. - Atherosclerosis 12: 1-14 (1970).
14. (a) Björkhem I., Andersson O., Diczfalusy U., Sevastik B., Xiu R.J., Duan C., and Lund E. -Proc. Natl. Acad. Sci. U.S.A. 91: 8592-8596 (1994).
15. (b) Lund E., Andersson O., Zhang J., Babiker A., Ahlborg G., Diczfalusy U., Einarsson K., Sjövall J., and Björkhem I. - Thromb. Vasc. Biol. 16: 208-212 (1996).
16. (c) Babiker A., Andersson O., Lund E., Xiu R.-J., Deeb S., Reshef A., Leitersdorf E., Diczfalusy U., and Björkhem I. - J. Biol. Chem. 272: 26253-26261 (1997).
17. (d) Reiss A.B., Martin K.O., Rojer D.E., Iyer S., Grossi E.A., Galloway A.C., and Javitt N.B. - J. Lipid Res. 38: 1254-1260 (1997).
18. Swaminathan S., Wilson W.K., Pinkerton F.D., Gerst N., Ramser M., and Schroepfer G.J., Jr. -J. Lipid Res. 34: 1805-1823 (1993).
19. Note that an important correction was made to this work: (a) Su X., Siddiqui A.U., Swaminathan S., Wilson W.K., and Schroepfer G.J., Jr. - J. Labelled Cmpd. Radiopharm. 41, 253-254 (1998), Erratum.
20. (b) Su X., Siddiqui A.U., Swaminathan S., Wilson W.K., and Schroepfer G.J., Jr. - J. Labelled Cmpd. Radiopharm. 41: 63-74 (1998).
21. Siddiqui A.U., Swaminathan S., Su X., Wilson W.K., and Schroepfer G.J., Jr. - Chem. Phys. Lipids, 86: 95-119 (1997).
22. Swaminathan S., Siddiqui A.U., Gerst N., Pinkerton F.D., Kisic A., Kim L.J., Wilson W.K., and Schroepfer G.J., Jr. - J. Lipid Res. 36: 767-786 (1995).
23. Carroll, J.N., Pinkerton, F.D., Su, X., Gerst, N., Wilson, W.K., and Schroepfer, G.J., Jr. -Chem. Phys. Lipids 94: 209-225 (1998).
24. 1H triplet at δ 0.93. This signal would be obscured in 6b by the H-21 doublet (δ 0.94), but traces of tributyltin would be observable as multiplets at δH 1.30 and 1.36 (in open spectral regions of 6b at 500 MHz) and in the COSYDEC spectrum (notably at δ 0.93). After MPLC purification of 6b, no trace of tributyltin signals were observed in its NMR spectra. The relative ease of removal of tributyltin materials compared with similar reduction of a 15-ketosterol (7) is attributable to the very low loading on the MPLC column described herein.
25. Wilson W.K., Sumpter R.M., Warren J.J., Rogers P.S., Ruan B., and Schroepfer G.J., Jr. - J. Lipid Res. 37: 1529-1555 (1996).
26. (a) These calculations are based on NMR data of higher precision than those given in previously (5, 12b) for 6a. The observed isotope shifts represent weighted averages of isotope shifts for the 23R-and 23S-deuterio species.
27. (b) Gerst N., Pinkerton F.D., Kisic A., Wilson W.K., Swaminathan S., and Schroepfer G.J., Jr. - J. Lipid Res. 35: 1040-1056 (1994).
28. Wyllie S.G., Amos B.A., and Tökés L. - J. Org. Chem. 42: 725-732 (1977).
29. 3H of the sodium borotritide described herein were those provided by the commercial supplier.
30. 3 were observed for most signals in rings A and B of diol 2.
31. The structure elucidation of the 3β,23-diols and their characterization by NMR will be presented elsewhere.