title: Efficient production of [n]rotaxanes by using template-directed clipping reactions.
abstract: In this article, we report on the efficient synthesis of well defined, homogeneous [n]rotaxanes (n up to 11) by a template-directed thermodynamic clipping approach. By employing dynamic covalent chemistry in the form of reversible imine bond formation, [n]rotaxanes with dialkylammonium ion (-CH(2)NH(2)(+)CH(2)-) recognition sites, encircled by [24]crown-8 rings, were prepared by a thermodynamically controlled, template-directed clipping procedure, that is, by mixing together a dumbbell compound containing a discrete number of CH(2)NH(2)(+)CH(2)- ion centers with appropriate amounts of a dialdehyde and a diamine to facilitate the [n]rotaxane formation. A 21-component self-assembly process is operative during the formation of the [11]rotaxane. The oligomeric dumbbells containing CH(2)NH(2)(+)CH(2)- ion recognition sites were prepared by a stepwise protocol. Several of the dynamic [n]rotaxanes were converted into their kinetically stable counterparts, first by reduction ("fixing") of imine bonds with the BH(3).THF complex, then by protonation of the complex by addition of acid.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, 405 Hilgard Avenue, Los Angeles, CA 90095, USA.
authors.forename: Jishan
authors.initials: J
authors.lastname: Wu
authors.forename: Ken Cham-Fai
authors.initials: KC
authors.lastname: Leung
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
mesh_terms: D005561:Formates / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D043862:Rotaxanes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D005561:Formates; D043862:Rotaxanes; C030544:formic acid