Functionalized benzocyclotrimers : stereocontrolled synthesis and supramolecular applications

Benzocyclotrimers are polycyclic compounds which can be obtained through self-coupling reactions of bicyclic olefins. This work presents the optimization of a new method for the synthesis of cyclotrimers using a feasible procedure based on the Heck-type self-coupling reaction of enantiopure iodobornenes. The screening and the optimization of several functionalization reactions led to the preparation of covalent supramolecular hosts and self-assembling derivatives. In particular, the condensation of benzotricamphor with aliphatic diamines provided imine-linked molecular cages which exhibited hosting properties for small neutral guests. On the other hand, coupling reactions of benzotricamphor triflate with terminal alkynes provided new self-assembling derivatives based on metal-ligand, H-bonding and ionic interactions. The research of other functionalization reactions for benzocyclotrimers helpfully led to a new general method for the synthesis of disubstituted arylacetylenes from aryl bromides based on decarboxylative coupling reactions of acetylene carboxylic acid.