Effect of Chain Length on Radical to Carbanion Cyclo-Coupling of Bromoaryl Alkyl-Linked Oxazolines: 1,3-Areneotropic Migration of Oxazolines

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Abstract

2-Halophenylalkyl-2-oxazolines with alkyl chain spacers of two to six C atoms (n = 0-4) were prepared and their S(RN)1-type reactions with several base systems examined. The best conditions to promote cyclo-coupling to the corresponding benzocycloalkane derivatives involved use of LDA in THF. The precursors with 3-C-atom and 4-C-atom spacers gave good yields of 2-(1'-phenylindan-1'-yl)-2-oxazolines and 2-(1-phenyl-1,2,3,4-tetrahydronaphthalen-1-yl)-2-oxazoline, respectively. The major products from the precursor with a 5-C-atom spacer were derivatives of benzocycloheptane in which the oxazoline group had undergone a novel areneotropic migration from the end of the spacer to the benzo ring. The product from reaction of the corresponding 2-C-atom precursor was a 9-oxazolinophenanthrene derivative. EPR spectroscopy showed the intermediates of the LDA-promoted reactions to be radical anions of the product benzocycloalkanes. This supported an S(RN)1-type chain mechanism involving initial production of aryl radicals connected to azaenolate ions via the spacer groups. Intramolecular radical to carbanion coupling then generated ring-closed benzocycloalkane radical anions that transferred an electron to more precursor. Diastereoselective radical to carbanion cyclo-coupling reactions were carried out with 2-bromophenylpropyl precursors containing chiral 2-oxazolines. The diastereoselectivity achievable was modest, but the product diastereoisomeric Indane derivatives were easily separable by chromatography.

Original languageEnglish
Pages (from-to)898-911
Number of pages14
JournalThe Journal of Organic Chemistry
Volume72
Issue number3
DOIs
Publication statusPublished - 2 Feb 2007

Keywords

  • VINYLOGOUS MANNICH REACTIONS
  • ELECTRON SPIN RESONANCE
  • NUCLEOPHILIC-SUBSTITUTION
  • HOMOLYTIC SUBSTITUTION
  • S(RN)1 MECHANISM
  • CYCLIZATIONS
  • CHLORANILINES
  • DERIVATIVES
  • REACTIVITY
  • DIANIONS

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