Efficient production of [n]rotaxanes by using template-directed clipping reactions.

Jishan Wu, Ken Cham-Fai Leung, J Fraser Stoddart

Index: Proc. Natl. Acad. Sci. U. S. A. 104(44) , 17266-71, (2007)

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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.