TY - JOUR
T1 - Conformational isomerism in and binding properties to alkali-metals and an ammonium salt of O-alkylated homooxacalix[3]arenes.
AU - Araki, Koji
AU - Inada, Kousuke
AU - Otsuka, Hideyuki
AU - Shinkai, Seiji
PY - 1993
Y1 - 1993
N2 - 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.
AB - 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.
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U2 - 10.1016/S0040-4020(01)80216-7
DO - 10.1016/S0040-4020(01)80216-7
M3 - Article
AN - SCOPUS:0027375960
VL - 49
SP - 9465
EP - 9478
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 42
ER -