Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes

Peter R. Ashton, Aaron M. Heiss, Dario Pasini, Francisco Raymo, Andrew N. Shipway, J. Fraser Stoddart, Neil Spencer

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Two chiral π-electron-rich crown ethers incorporating either a binaphthol or two D-mannitol units have been synthesized and their abilities to bind bipyridinium guests demonstrated. Both crown ethers could be interlocked mechanically with cyclobis(paraquat-p-phenylene) to afford two chiral [2]catenanes. Furthermore, these crown ethers were also mechanically interlocked with a tetracationic cyclophane incorporating a 2,2'-dihydroxy- 1,1'-binaphthyl spacer to afford mixtures of diastereoisomeric [2]catenanes. The composition of these mixtures was determined by 1H-NMR-spectroscopic and HPLC analyses which revealed that modest diastereoselection (56:44-67:33) occurs during the kinetically controlled self-assembly of the catenanes. The free energy barriers (12.8-16.8 kcal mol-1) associated with the circumrotation of one macrocyclic component through the cavity of the other and vice versa were determined by variable-temperature 1H-NMR spectroscopy. In addition, another dynamic process involving the 'rocking' of the mean planes of the mechanically interlocked macrocycles with respect to each other was also identified and the associated free energy barriers (10.3-10.4 kcal mol-1) determined.

Original languageEnglish
Pages (from-to)995-1004
Number of pages10
JournalEuropean Journal of Organic Chemistry
Issue number5
StatePublished - May 1 1999
Externally publishedYes

Fingerprint

Catenanes
Crown Ethers
Self assembly
self assembly
ethers
Energy barriers
Free energy
free energy
mannitol
nuclear magnetic resonance
Paraquat
Mannitol
spacers
Nuclear magnetic resonance spectroscopy
Nuclear magnetic resonance
cavities
Electrons
Chemical analysis
spectroscopy
electrons

Keywords

  • Catenanes
  • Diastereoselectivity
  • Molecular Recognition
  • Self- Assembly
  • Template-Directed Synthesis

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Ashton, P. R., Heiss, A. M., Pasini, D., Raymo, F., Shipway, A. N., Stoddart, J. F., & Spencer, N. (1999). Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes. European Journal of Organic Chemistry, (5), 995-1004.

Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes. / Ashton, Peter R.; Heiss, Aaron M.; Pasini, Dario; Raymo, Francisco; Shipway, Andrew N.; Stoddart, J. Fraser; Spencer, Neil.

In: European Journal of Organic Chemistry, No. 5, 01.05.1999, p. 995-1004.

Research output: Contribution to journalArticle

Ashton, PR, Heiss, AM, Pasini, D, Raymo, F, Shipway, AN, Stoddart, JF & Spencer, N 1999, 'Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes', European Journal of Organic Chemistry, no. 5, pp. 995-1004.
Ashton PR, Heiss AM, Pasini D, Raymo F, Shipway AN, Stoddart JF et al. Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes. European Journal of Organic Chemistry. 1999 May 1;(5):995-1004.
Ashton, Peter R. ; Heiss, Aaron M. ; Pasini, Dario ; Raymo, Francisco ; Shipway, Andrew N. ; Stoddart, J. Fraser ; Spencer, Neil. / Molecular meccano, 51. - Diastereoselective self-assembly of [2]catenanes. In: European Journal of Organic Chemistry. 1999 ; No. 5. pp. 995-1004.
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