Selectfluor as a Nucleofuge in the Reactions of Azabicyclo[n.2.1]alkane β-Halocarbamic Acid Esters (n = 2,3)

• Published in: Journal of organic chemistry Vol. 73; no. 6; pp. 2122 - 2129
• Main Authors: Krow, Grant R, Gandla, Deepa, Guo, Weiwei, Centafont, Ryan A, Lin, Guoliang, DeBrosse, Charles, Sonnet, Philip E, Ross, Charles W, Ramjit, Harri G, Cannon, Kevin C
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 21.03.2008; Amer Chemical Soc
• Subjects: Azabicyclo Compounds - chemistry; Carbamates - chemistry; Chemical reactivity; Chemistry; Chemistry, Organic; Diazonium Compounds - chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Hydrocarbons, Halogenated - chemistry; Hydrolysis; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; REARRANGEMENT ROUTE; MEDIATED REARRANGEMENT; MERCURY(II) OXIDE; FORMAL SYNTHESIS; HYDROGEN-BOND; CHLOROSULFONYL ISOCYANATE; ORGANIC-COMPOUNDS; STEREOSPECIFIC ROUTE; FLUORINE; NEIGHBORING GROUP PARTICIPATION; Haloalcohol; Nitrogen heterocycle; NMR spectrometry; Sodium bromide; Stereochemistry; Sodium chloride; Haloketone; Organic halogen compounds; Sodium iodide; Hydrolysis; Ester; Organic fluorine compounds; Mercury II Fluorides; Bicyclic compound; Oxidation; Chemical reactivity
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo702155v

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.