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

Research output: Contribution to journalArticle

81 Citations (Scopus)

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

Fingerprint

Isomerism
Alkali Metals
Ammonium Compounds
Thermodynamics
Cations
Cones
Magnetic Resonance Spectroscopy
Salts
High Pressure Liquid Chromatography
Oxygen
Proton Magnetic Resonance Spectroscopy
Reaction intermediates

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Cite this

Conformational isomerism in and binding properties to alkali-metals and an ammonium salt of O-alkylated homooxacalix[3]arenes. / Araki, Koji; Inada, Kousuke; Otsuka, Hideyuki; Shinkai, Seiji.

In: Tetrahedron, Vol. 49, No. 42, 01.01.1993, p. 9465-9478.

Research output: Contribution to journalArticle

Araki, Koji ; Inada, Kousuke ; Otsuka, Hideyuki ; Shinkai, Seiji. / Conformational isomerism in and binding properties to alkali-metals and an ammonium salt of O-alkylated homooxacalix[3]arenes. In: Tetrahedron. 1993 ; Vol. 49, No. 42. pp. 9465-9478.
@article{009aa694936247d28fa03d0a80fc68c9,
title = "Conformational isomerism in and binding properties to alkali-metals and an ammonium salt of O-alkylated homooxacalix[3]arenes.",
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.",
author = "Koji Araki and Kousuke Inada and Hideyuki Otsuka and Seiji Shinkai",
year = "1993",
month = "1",
day = "1",
doi = "10.1016/S0040-4020(01)80216-7",
language = "English",
volume = "49",
pages = "9465--9478",
journal = "Tetrahedron",
issn = "0040-4020",
publisher = "Elsevier Limited",
number = "42",

}

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 - 1993/1/1

Y1 - 1993/1/1

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.

UR - http://www.scopus.com/inward/record.url?scp=0027375960&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0027375960&partnerID=8YFLogxK

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 -