Template-Directed Dynamic Synthesis of Mechanically Interlocked Dendrimers

Abstract

The versatility and efficiency of dynamic covalent chemistry (DCC) has been exploited in the convergent synthesis of mechanically interlocked dendrimers that are based upon the mutual recognition expressed between secondary dialkylammonium ions and crown ether-like macrocycles. Reversible imine bond formation is employed to clip two acyclic fragments, one of them a diformylpyridine unit bearing a dendritic side chain, and the other a complementary dianiline in the shape of the di(o-aminophenyl)ether of tetraethylene glycol, around each arm of a tritopic trisammonium ion core, thereby affording a branched [4]rotaxane. This template-directed strategy has been demonstrated to work in very high yields (>90%) with successive generations (G0-G2) of a modified Fréchet-type dendritic wedge attached to the 4-position of the diformylpyridine unit. Reduction of these dynamic dendritic systems is achieved upon treatment with borane.THF and results in kinetically stable compounds. The inherent modularity of the overall process should allow for the rapid and straightforward access to many other analogous mechanically interlocked systems in which either the branched core or the dendritic periphery can be modified to suit the needs of any given application of these molecules. Indeed, the dynamic nature of the initial thermodynamically mediated assembly could be utilized in order to amplify particular products from a potential library as a result of a selective recognition process.