Highly selective and high-yielding rotaxane synthesis via aminolysis of prerotaxanes consisting of a ring component and a stopper unit.

A highly rotaxane-selective synthesis via aminolysis of prerotaxanes, which were composed of a phenolic pseudo-crown ether as a ring component and a bulky stopper unit, was developed. The best result was obtained in the case of aminolysis of 3b with 3,5-dimethylbenzylamine which proceeded quantitatively with ca. 100% rotaxane selectivity forming the corresponding rotaxane 5b. The rotaxanes were formed by kinetically controlled attack of the amine from the backside of the ring component of the prerotaxanes.