Preorganized ligand arrays based on spirotetrahydrofuranyl motifs. Synthesis of the steyeoisomeric 1,8,14-trioxatrispiro[4.1.4.1.4.1]octadecanes and the contrasting conformational features and ionic binding capacities of these belted ionophores

L. A. Paquette, J. Tae, E. R. Hickey, W. E. Trego, R. D. Rogers

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Abstract

The cis,trans trispiro ether 4 is accessible from several synthetic directions as a consequence of a crossover in reaction selectivity when proceeding from nucleophilic attack on the cis dispiro ketone to oxygenation of the α,β-unsaturated ester 17. Its cis,cis isomer 3 was obtained in 17 steps and 14.6% overall yield from 3,5-dimethoxybenzoic acid by making use of the alicyclic side chain in N as a "conformational lock". Although 4 shows no measurable tendency to complex with alkali metal ions, 3 binds strongly to Li+ and Na+ ions, as well as to CH3NH3+. Whereas the 3eq conformation is populated in the solid state and in solution, complex formation occurs readily. 13C NMR studies have defined slow exchange limits as the 2:1 sandwich complex with lithium ion is initially formed and transformed progressively into a 1:1 species upon the addition of more LiClO4. Only the 2:1 complex with sodium ion is formed during comparable titration with NaClO4. Association constants, molecular mechanics calculations, and X-ray crystallographic studies provide insight into the binding capacity of this belted tridentate ionophore.

Original languageEnglish
Pages (from-to)9160-9171
Number of pages12
JournalJournal of Organic Chemistry
Volume65
Issue number26
DOIs
Publication statusPublished - 2000 Dec 29

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Ionophores
Ions
Ligands
Alkali Metals
Molecular mechanics
Oxygenation
Ketones
Titration
Lithium
Isomers
Ether
Metal ions
Conformations
Esters
Sodium
Nuclear magnetic resonance
X rays
Acids
octadecane

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

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title = "Preorganized ligand arrays based on spirotetrahydrofuranyl motifs. Synthesis of the steyeoisomeric 1,8,14-trioxatrispiro[4.1.4.1.4.1]octadecanes and the contrasting conformational features and ionic binding capacities of these belted ionophores",
abstract = "The cis,trans trispiro ether 4 is accessible from several synthetic directions as a consequence of a crossover in reaction selectivity when proceeding from nucleophilic attack on the cis dispiro ketone to oxygenation of the α,β-unsaturated ester 17. Its cis,cis isomer 3 was obtained in 17 steps and 14.6{\%} overall yield from 3,5-dimethoxybenzoic acid by making use of the alicyclic side chain in N as a {"}conformational lock{"}. Although 4 shows no measurable tendency to complex with alkali metal ions, 3 binds strongly to Li+ and Na+ ions, as well as to CH3NH3+. Whereas the 3eq conformation is populated in the solid state and in solution, complex formation occurs readily. 13C NMR studies have defined slow exchange limits as the 2:1 sandwich complex with lithium ion is initially formed and transformed progressively into a 1:1 species upon the addition of more LiClO4. Only the 2:1 complex with sodium ion is formed during comparable titration with NaClO4. Association constants, molecular mechanics calculations, and X-ray crystallographic studies provide insight into the binding capacity of this belted tridentate ionophore.",
author = "Paquette, {L. A.} and J. Tae and Hickey, {E. R.} and Trego, {W. E.} and Rogers, {R. D.}",
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T1 - Preorganized ligand arrays based on spirotetrahydrofuranyl motifs. Synthesis of the steyeoisomeric 1,8,14-trioxatrispiro[4.1.4.1.4.1]octadecanes and the contrasting conformational features and ionic binding capacities of these belted ionophores

AU - Paquette, L. A.

AU - Tae, J.

AU - Hickey, E. R.

AU - Trego, W. E.

AU - Rogers, R. D.

PY - 2000/12/29

Y1 - 2000/12/29

N2 - The cis,trans trispiro ether 4 is accessible from several synthetic directions as a consequence of a crossover in reaction selectivity when proceeding from nucleophilic attack on the cis dispiro ketone to oxygenation of the α,β-unsaturated ester 17. Its cis,cis isomer 3 was obtained in 17 steps and 14.6% overall yield from 3,5-dimethoxybenzoic acid by making use of the alicyclic side chain in N as a "conformational lock". Although 4 shows no measurable tendency to complex with alkali metal ions, 3 binds strongly to Li+ and Na+ ions, as well as to CH3NH3+. Whereas the 3eq conformation is populated in the solid state and in solution, complex formation occurs readily. 13C NMR studies have defined slow exchange limits as the 2:1 sandwich complex with lithium ion is initially formed and transformed progressively into a 1:1 species upon the addition of more LiClO4. Only the 2:1 complex with sodium ion is formed during comparable titration with NaClO4. Association constants, molecular mechanics calculations, and X-ray crystallographic studies provide insight into the binding capacity of this belted tridentate ionophore.

AB - The cis,trans trispiro ether 4 is accessible from several synthetic directions as a consequence of a crossover in reaction selectivity when proceeding from nucleophilic attack on the cis dispiro ketone to oxygenation of the α,β-unsaturated ester 17. Its cis,cis isomer 3 was obtained in 17 steps and 14.6% overall yield from 3,5-dimethoxybenzoic acid by making use of the alicyclic side chain in N as a "conformational lock". Although 4 shows no measurable tendency to complex with alkali metal ions, 3 binds strongly to Li+ and Na+ ions, as well as to CH3NH3+. Whereas the 3eq conformation is populated in the solid state and in solution, complex formation occurs readily. 13C NMR studies have defined slow exchange limits as the 2:1 sandwich complex with lithium ion is initially formed and transformed progressively into a 1:1 species upon the addition of more LiClO4. Only the 2:1 complex with sodium ion is formed during comparable titration with NaClO4. Association constants, molecular mechanics calculations, and X-ray crystallographic studies provide insight into the binding capacity of this belted tridentate ionophore.

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