2006
DOI: 10.1021/jo060829h
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Template Synthesis of [2]Rotaxanes with Large Ring Components and Tris(biphenyl)methyl Group as the Blocking Group. The Relationship between the Ring Size and the Stability of the Rotaxanes

Abstract: We synthesized a series of macrocyclic phenanthrolines 3a-e and a tris(biphenyl)methyl derivative 4. [2]Rotaxanes with large ring components (10a,b) were synthesized by the template method, and the stability of the rotaxanes was examined. The study revealed that the tris(biphenyl)methyl group is an effective blocking group for the rotaxanes with up to a 33-membered ring. Even a rotaxane with a 37-membered macrocyclic phenanthroline (10b) could be isolated. The dissociation of 10b occurred at 60 degrees C.

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Cited by 35 publications
(33 citation statements)
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“…The half-lives for the [3]rotaxane (t 1/2 = ln 2/k; k: rate constant for the dissociation reaction of Fig. 7) is around 200 h at 298 K whereas it is approximately 50 h at 333 K. Although direct comparison to other systems [35] is impossible, it must be noted that the enthalpic contribution ( H ‡ ) to the unthreading barrier is rather low whereas the entropic component (k ∞ and S ‡ ) is remarkably high: H ‡ = 33 ± 3 kJ mol −1 and S ‡ = −182 ± 55 J K −1 mol −1 , from which G ‡ (298 K) = 87 ± 9 kJ mol −1 was deduced. The high activation entropy indicates that the unthreading reaction has a highly ordered transition state, i.e., it is strongly dependent on the relative orientation of the ring and the two strings.…”
Section: Demetalation Of the Cobalt(ii)-complexed [3]rotaxane And Stumentioning
confidence: 96%
“…The half-lives for the [3]rotaxane (t 1/2 = ln 2/k; k: rate constant for the dissociation reaction of Fig. 7) is around 200 h at 298 K whereas it is approximately 50 h at 333 K. Although direct comparison to other systems [35] is impossible, it must be noted that the enthalpic contribution ( H ‡ ) to the unthreading barrier is rather low whereas the entropic component (k ∞ and S ‡ ) is remarkably high: H ‡ = 33 ± 3 kJ mol −1 and S ‡ = −182 ± 55 J K −1 mol −1 , from which G ‡ (298 K) = 87 ± 9 kJ mol −1 was deduced. The high activation entropy indicates that the unthreading reaction has a highly ordered transition state, i.e., it is strongly dependent on the relative orientation of the ring and the two strings.…”
Section: Demetalation Of the Cobalt(ii)-complexed [3]rotaxane And Stumentioning
confidence: 96%
“…This metal has been extensively used as a template in our group [1b, 18] or in other research teams. [19][20][21] Other transition-metal centers have also been used successfully in the templated synthesis of various catenanes and rotaxanes. [22][23][24][25][26] Organic templates, assembled via formation of aromatic acceptor-donor complexes and/or hydrogen bonds, have also been very successful.…”
Section: Introductionmentioning
confidence: 99%
“…[143] Saito erforschte die Grenzen zwischen Rotaxanen und Pseudorotaxanen, indem er mit einem Cu I (dpp) 2 -Templat und großen (33-bis 45-gliedrigen) Makrocyclen Rotaxane bildete. [144] Sauvage und Diederich befestigten durch eine oxidative Acetylenkupplung (unter der Verwendung des Vorläufers in Schema 11 b) kovalent Fullerene und stellten so [2]Rotaxane zur Untersuchung elektrochemischer und photoinduzierter Prozesse her. [145] Eine interessante Eigenschaft verschlungener Moleküle ist deren Potenzial zur Bildung topologisch chiraler Strukturen.…”
Section: Angewandte Chemieunclassified