Selectfluor as a nucleofuge in the reactions of azabicyclo[n.2.1]alkane beta-halocarbamic acid esters (n = 2,3).
The ability of Selectfluor to act as a nucleofuge for hydrolysis of beta-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 HgF(2) 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.
Krow
Grant R
GR
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA. grantkrow@aol.com
Gandla
Deepa
D
Guo
Weiwei
W
Centafont
Ryan A
RA
Lin
Guoliang
G
Debrosse
Charles
C
Sonnet
Philip E
PE
Ross
Charles W
CW
Ramjit
Harri G
HG
Cannon
Kevin C
KC
D053961:Azabicyclo Compounds / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D003979:Diazonium Compounds / Q000737:chemistry*; D006846:Hydrocarbons, Halogenated / Q000737:chemistry; D006868:Hydrolysis
D053961:Azabicyclo Compounds; D002219:Carbamates; D003979:Diazonium Compounds; D006846:Hydrocarbons, Halogenated; C408750:selectfluor