Self-assembling cyclophanes and catenanes possessing elements of planar chirality

Peter R. Ashton, Sue E. Boyd, Stephan Menzer, Dario Pasini, Francisco Raymo, Neil Spencer, J. Fraser Stoddart, Andrew J P White, David J. Williams, Paul G. Wyatt

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Cyclobis(paraquat-1,5-naphthalene) has been prepared by a template-directed synthesis. As a result of the presence of the two chiral planes generated by its 1,5-disubstituted naphthalene residues, this compound can exist in three different stereoisomeric forms, an achiral (RS) form and two chiral forms, (RR) and (SS). Although the racemic modification could not be separated from the meso isomer, dynamic NMR spectroscopy together with molecular modeling indicate a diastereoisomeric ratio of 3:1 in favor of the (RR/SS) form. In addition, a couple of [2]catenanes in which the π-electron-deficient cyclobis(paraquat-1,5-naphthalene) component is interlocked with one of the π-electron-rich macrocyclic polyethers bis-p-phenylene[34]crown-10 (BPP34C10) or bis-1/5-dinaphtho[38]crown-10 (1/5DN38C10) self-assemble with diastereoselectivities in the range 50-60%. Relative stereochemical assignments for the different stereoisomeric forms have been achieved by dynamic NMR spectroscopy. In both [2]catenanes, the diastereoisomers in which the tetracationic cyclophanes have local D2 symmetry predominate. When the dynamic processes occurring within the [2]catenane containing the 1/5DN38C10 macrocycle are slow on the NMR timescale, a third element of planar chirality can be observed. This element is associated with the inside 1,5-dioxynaphthalene residue belonging to the crown ether and is orthogonal to the two chiral planes already present within the skeleton of the tetracationic cyclophane component. After repeated fractional crystallizations, single crystals were obtained, and one was subjected to X-ray crystallography. The 1,5-disubstituted naphthalene residues in both the cyclobis(paraquat-1,5-naphthalene) and the 1/5DN38C10 components were found to have (SS) chirality; that is, the [2]catenane undergoes spontaneous resolution on crystallization.

Original languageEnglish
Pages (from-to)299-310
Number of pages12
JournalChemistry - A European Journal
Volume4
Issue number2
DOIs
StatePublished - Feb 1 1998
Externally publishedYes

Fingerprint

Catenanes
Chirality
Naphthalene
Paraquat
Crystallization
Nuclear magnetic resonance spectroscopy
Crown Ethers
Crown ethers
Molecular modeling
Electrons
Polyethers
X ray crystallography
Isomers
Nuclear magnetic resonance
naphthalene
Single crystals
1,5-dinaphtho-38-crown-10

Keywords

  • Catenanes
  • Chirality
  • Pseudorotaxanes
  • Self-assembly
  • Template synthesis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Self-assembling cyclophanes and catenanes possessing elements of planar chirality. / Ashton, Peter R.; Boyd, Sue E.; Menzer, Stephan; Pasini, Dario; Raymo, Francisco; Spencer, Neil; Stoddart, J. Fraser; White, Andrew J P; Williams, David J.; Wyatt, Paul G.

In: Chemistry - A European Journal, Vol. 4, No. 2, 01.02.1998, p. 299-310.

Research output: Contribution to journalArticle

Ashton, PR, Boyd, SE, Menzer, S, Pasini, D, Raymo, F, Spencer, N, Stoddart, JF, White, AJP, Williams, DJ & Wyatt, PG 1998, 'Self-assembling cyclophanes and catenanes possessing elements of planar chirality', Chemistry - A European Journal, vol. 4, no. 2, pp. 299-310. https://doi.org/10.1002/(SICI)1521-3765(19980210)4:2<299::AID-CHEM299>3.0.CO;2-Z
Ashton, Peter R. ; Boyd, Sue E. ; Menzer, Stephan ; Pasini, Dario ; Raymo, Francisco ; Spencer, Neil ; Stoddart, J. Fraser ; White, Andrew J P ; Williams, David J. ; Wyatt, Paul G. / Self-assembling cyclophanes and catenanes possessing elements of planar chirality. In: Chemistry - A European Journal. 1998 ; Vol. 4, No. 2. pp. 299-310.
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AU - Spencer, Neil

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N2 - Cyclobis(paraquat-1,5-naphthalene) has been prepared by a template-directed synthesis. As a result of the presence of the two chiral planes generated by its 1,5-disubstituted naphthalene residues, this compound can exist in three different stereoisomeric forms, an achiral (RS) form and two chiral forms, (RR) and (SS). Although the racemic modification could not be separated from the meso isomer, dynamic NMR spectroscopy together with molecular modeling indicate a diastereoisomeric ratio of 3:1 in favor of the (RR/SS) form. In addition, a couple of [2]catenanes in which the π-electron-deficient cyclobis(paraquat-1,5-naphthalene) component is interlocked with one of the π-electron-rich macrocyclic polyethers bis-p-phenylene[34]crown-10 (BPP34C10) or bis-1/5-dinaphtho[38]crown-10 (1/5DN38C10) self-assemble with diastereoselectivities in the range 50-60%. Relative stereochemical assignments for the different stereoisomeric forms have been achieved by dynamic NMR spectroscopy. In both [2]catenanes, the diastereoisomers in which the tetracationic cyclophanes have local D2 symmetry predominate. When the dynamic processes occurring within the [2]catenane containing the 1/5DN38C10 macrocycle are slow on the NMR timescale, a third element of planar chirality can be observed. This element is associated with the inside 1,5-dioxynaphthalene residue belonging to the crown ether and is orthogonal to the two chiral planes already present within the skeleton of the tetracationic cyclophane component. After repeated fractional crystallizations, single crystals were obtained, and one was subjected to X-ray crystallography. The 1,5-disubstituted naphthalene residues in both the cyclobis(paraquat-1,5-naphthalene) and the 1/5DN38C10 components were found to have (SS) chirality; that is, the [2]catenane undergoes spontaneous resolution on crystallization.

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KW - Pseudorotaxanes

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