An Approach to Thermodynamically Controlled Supramolecular Assembly Possessing an Integral Locking Mechanism

A general approach for thermodynamically controlled molecular assembly employing carbonyl addition chemistry is exemplified with a prototypical rotaxane synthesis. Recognition−driven assembly of the rotaxane proceeds under conditions of mild base catalysis, while subsequent treatment with catalytic acid triggers a dehydrative locking mechanism and fixes the evolved molecular architecture in place.