Conformational isomerism in and binding properties to alkali-metals and an ammonium salt of O-alkylated homooxacalix[3]arenes.

Koji Araki, Kousuke Inada, Hideyuki Otsuka, Seiji Shinkai

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Abstract

7,15,23-Tri-tert-butyl-25,26,27-trihydroxy-2,3,10,11,18,19-hexahomo-3,11,19-trioxacalix[3]arene (1H3) was tri-O-alkylated with alkyl halides (RX: R=Me, Et, n-Pr, and n-Bu) in the presence of various bases and the products (1R3) were analyzed by HPLC and 1H NMR spectroscopy. It was found that (i) ring inversion which occurs through the oxygen-through-the-annulus rotation is allowed for 1Me3, 1Et3, and 1Pr3 whereas it is inhibited for 1Bu3, (ii) the cone/partial-cone equilibrium in 1Et3 and 1Pr3 is predominantly inclined to partial-cone, indicating the thermodynamic stability of partial-cone conformers, and (iii) in the product distribution of 1Bu3 partial-cone is yielded in preference for cone, indicating the kinetic preference for partial-cone. From the analysis of the reaction intermediates the possible reaction routes to cone- and partial-cone-1Bu3 are discussed. 1R3 showed the selectivity toward K+ among alkali metal cations and the cone conformers had the extractability (Ex%) higher than the partial-cone conformers. Cone-1R3 showed the high affinity for BuNH3+ because of (averaged) C3 symmetry common to both cone-1R3 host and BuNH3+ guest.

Original languageEnglish
Pages (from-to)9465-9478
Number of pages14
JournalTetrahedron
Volume49
Issue number42
DOIs
Publication statusPublished - Jan 1 1993

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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