(Chemical Equation Presented) The ability of Selectfluor to act as a nucleofuge for hydrolysis of β;-anti-halides was investigated with N-alkoxycarbonyl derivatives of 6-anti/-Y-7-anti/-X-2-azabicyclo[2.2.1]heptanes and 4-anti-Y-8-anti-X-6-azabicyclo[3.2.1]octanes. The azabicycles contained X = I or Br groups in the methano bridge and Y = F, Br, Cl, or OH substituents in the larger bridge. The relative reactivities of the halides were a function of the azabicycle, the halide, and its bridge and the addition of Selectfluor or HgF2 as a nucleofuge. All halide displacements occurred with retention of stereochemistry. Selectfluor with sodium bromide or sodium chloride, but not sodium iodide, competitively oxidized some haloalcohols to haloketones. A significant 15.6 Hz F⋯HO NMR coupling was observed with 4-anti/-fluoro-8-anti/-hydroxy-6-azabicyclo-[3.2.1]octane.
All Science Journal Classification (ASJC) codes
- Organic Chemistry