Triethylamine poly(hydrogen fluorides) in the synthesis of a fluorinated nucleoside glycon

Tetrahedron Letters

Volumn 37, Issue 1, 1996, Pages 17-20

  Chou, T S ^a   Becke, Lisa M ^a   O'Toole, John C ^a   Carr, M Austin ^a   Parker, Bruce E ^a  

^a ELI LILLY AND COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEOSIDE DERIVATIVE; ORGANOFLUORINE DERIVATIVE;

ARTICLE; FLUORINATION; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; TECHNIQUE;

EID: 0030066252     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(95)02102-7     Document Type: Article

References (17)

1. Fox, J.J.; Watanabe, K.A.; Chou, T.C.; Schinazi, R.F.; Soike, K.F.; Fourel, I.; Hantz, G.; Trepo, C. In Fluorinated Carbohydrates; Taylor, N.F., Ed.; American Chemical Society: Washington, D.C., 1988; pp 176-190 and references cited therein.
2. (a) Paar, D.P.; Hooton, T.M.; Smiles, K.A. Antimicrob Agents Chemother 1992, 264.
3. (b) Fried, F. W.; DiBisceglie, A.M.; Straus, S.E. Hepatology 1992, 16(4), 127A.
4. (a) Sallie, R.; Kleiner, D.; Richardson, F.; Conjeevaream, H.; Zullo, S.; Mutimer, D.; Hoover, S.; Fox, C.; Hoofnagle, J.H. Hepatology 1994, 20(4 part 2), 209A.
5. (b) Lau, D.; Mostoeski, H.; Hoofnagle, J.H.; Sallie, R. Hepatology 1994, 20 (4 part 2), 189A.
6. Reichman, U; Watanabe, K.A.; Fox, J. Carbohydr. Res. 1975, 42, 233.
7. (a) Brodfuehrer, P.R.; Sapino Jr., C.; Howell, H.G. J. Org. Chem. 1985, 50, 2597.
8. (b) Tann, C.H.; Brodfuehrer, P.R.; Brundidge, S.P.; Sapino Jr., C.; Howell, H.G. J. Org. Chem. 1985, 50, 3644.
9. (c) Howell, H.G.; Brodfuehrer, P.R.; Brundidge, S.P.; Benigni, D.A.; Sapino Jr., C. J. Org. Chem. 1988, 53, 85.
10. 3N·3HF is about 78 °C / 1.5 mbar. Franz, R. J. Fluorine Chem. 1980, 15, 423.
11. H.G. Howell and coworkers speculated that the fluorosulfonate (5) was the intermediate involved in their fluorination reaction using aqueous HF and KHF2 as the fluorinating agents (see reference 5b). The reactions in EtOAc and DCE were homogeneous and were run by the two-step method described. However, the fluorination in toluene was not homogeneous and was run at 70 °C only.
12. 2O gradient, 1.0 mL / min, λ = 230 nm, injection volume = 20 mL (Courtesy of David K. Robbins of LRL Chemical Process R & D).
13. 19F NMR are tetramethylsilane, chloroform and trichlorofluoromethane respectively.
14. 3N·xHF. Apparently, NaOH only titrates 2 out of 3 equivalents of the HF in the sample (Courtesy of Thomas K. Lobdell and Donald W. Hodges of LRL Chemical Process R & D).
15. Gennick, I.; Harmon, K.M.; Potvin, M.M. Inorg. Chem. 1977, 16, 2033.
16. Giudicelli, M.B.; Picq, D.; Veyron, B. Tetrahedron Lett. 1990, 31, 6527.
17. 3N.