Ricerc@Sapienza

This project is focused on the use of supramolecular catalysts in the H2O2-oxidation of aliphatic and aromatic C-H bonds. Such reaction is currently one of the most investigated chemical transformations in organic synthesis since it allows the direct installation of the desired function into the target molecule, with minimization of the number of synthetic steps and waste production. Furthermore the use of the environmentally friendly H2O2 offers the advantage of non-polluting reduction products.
In particular, in the first phase of the research, a complex based on White's PDP catalytic site, and endowed with benzo18crown6 moieties for the recognition of ammonium groups, already shown to possess unprecedented selectivity properties in the oxidation of primary ammonium ion with long aliphatic chain, will be tested as a supramolecular catalyst for the selective oxidation of substrates with biological interest such as derivatives of fatty acids and cholesterol, properly decorated with the ammonium anchoring group.
In the second phase of the research the effort of the team will be devoted to the realization of a new supramolecular catalyst, again based on a non-heme iron core as the catalytic site and on the benzo18crown6 ligand as the recognition site, but prepared with a different strategy. Using an innovative approach in the field of supramolecular catalysis, the possibility to mount the catalyst directly in the reaction mixture (in situ) without long and expansive synthetic procedure, will be investigated. The imine chemistry will be exploited both to i) assemble the iron catalytic core, an imine-based complex which is already known to efficiently catalyze the H2O2 oxidation of aliphatic and aromatic C-H bonds, ii) insert the recognition site for the binding of the ammonium anchoring group, which hopefully will confer to the catalyst the desired selectivity properties.