title: Neighboring group participation in the additions of iodonium and bromonium ions to N-alkoxycarbonyl-2-azabicyclo[2.2.n]alk-5-enes (n = 1,2).
abstract: Additions of iodonium-X reagents to N-alkoxycarbonyl-2-azabicyclo[2.2.1]hept-5-enes and the homologous 2-azabicyclo[2.2.2]oct-5-enes have been found to mirror the outcomes of additions of bromonium-X reagents. Only rearranged products were observed for reactions of either of these halonium ion reagents with the azabicylo[2.2.1]hept-5-enes. For the azabicyclo[2.2.2]oct-5-enes, nitrogen participation in addition of IOH or BrOH was dependent on the N-alkoxycarbonyl group. With larger N-Boc, N-Cbz, or N-Troc protecting groups, unrearranged 5-anti-hydroxy-6-syn-I(or Br)-2-azabicyclo[2.2.2]octanes were formed by nucleophilic attack at C(5) on syn-halonium ions. The structure of N-methyl-8-anti-bromo-4-anti-hydroxy-2-azabicyclo[3.2.1]octane has been reassigned by X-ray analysis.
authors.affiliation: Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, USA. grantkrow@aol.com
authors.forename: Grant R
authors.initials: GR
authors.lastname: Krow
authors.forename: Deepa
authors.initials: D
authors.lastname: Gandla
authors.forename: Weiwei
authors.initials: W
authors.lastname: Guo
authors.forename: Ryan A
authors.initials: RA
authors.lastname: Centafont
authors.forename: Guoliang
authors.initials: G
authors.lastname: Lin
authors.forename: Charles
authors.initials: C
authors.lastname: DeBrosse
authors.forename: Philip E
authors.initials: PE
authors.lastname: Sonnet
authors.forename: Charles W
authors.initials: CW
authors.lastname: Ross
authors.forename: Harri G
authors.initials: HG
authors.lastname: Ramjit
authors.forename: Patrick J
authors.initials: PJ
authors.lastname: Carroll
authors.forename: Kevin C
authors.initials: KC
authors.lastname: Cannon
mesh_terms: D053961:Azabicyclo Compounds / Q000737:chemistry*; D017605:Bromine Compounds / Q000737:chemistry; D003516:Cycloparaffins / Q000737:chemistry*; D017613:Iodine Compounds / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D009861:Onium Compounds / Q000737:chemistry*
chemical_list: D053961:Azabicyclo Compounds; D017605:Bromine Compounds; D003516:Cycloparaffins; D017613:Iodine Compounds; D009861:Onium Compounds