Selectfluor as a nucleofuge in the reactions of azabicyclo[n.2.1]alkane β-halocarbamic acid esters (n = 2,3)

Grant R. Krow, Deepa Gandla, Weiwei Guo, Ryan A. Centafont, Guoliang Lin, Charles DeBrosse, Philip E. Sonnet, Charles W. Ross, Harri G. Ramjit, Kevin C. Cannon

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Abstract

(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.

Original languageEnglish (US)
Pages (from-to)2122-2129
Number of pages8
JournalJournal of Organic Chemistry
Volume73
Issue number6
DOIs
Publication statusPublished - Mar 21 2008

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All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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