During the execution of NOVOCAT, considerable effort was devoted towards the synthesis of azanickelacycles and their reactivity with CO2 (objective 1). Although we managed to prepare some of these intermediates with a rather particular ligand backbone, CO2 insertion turned out not to be efficient enough to trigger the carboxylation event. This lack of reactivity is likely attributed to the non-innocent role of the ligand in this reaction, as the Martin group has observed that subtle differences on the ligand have a profound effect on reactivity. Unfortunately, the synthesis of other azanickelacycles possessing different ligand backbones was not possible. Similar discouraging results were observed when optimizing the catalytic reaction of aziridines with CO2 en route to β-amino acids. Although we made use of the HTE unit extensively, systematically analyzing the effect of the precatalyst, ligand, base, reductant, solvent and additives in a multidimensional manner, no reaction took place. Convinced about the relevance of a CO2 insertion into inert bonds, we switched our attention to the utilization of equally challenging scenario via C-F bond-cleavage. If successful, such pathway would potentially enable the possibility of promoting late-stage carboxylation techniques, thus changing fundamentally the properties of the drug, moving from a liphophilic environment (fluoride) to an hydrophilic motif (carboxylic acid). After extensive experimentation, it was serendipitously found that the presence of silylated reagents (initially perceived as vehicles towards the carboxylation event) triggered a previously unrecognized C-Si bond-forming event via C-F bond cleavage. (Scheme 1) Such a reaction can easily be extended to both aryl and alkyl series. Mechanistic experiments have been performed which demonstrate an abnormal nucleophilic substitution reaction over a rather strong C-F bond. We are currently finalizing the details of this reaction, and it is expected that the manuscript will be submitted to Angewandte Chemie within the next 1-2 months. It is worth noting that the group of Prof. Ruben Martin is still pursuing the carboxylation of aziridines according to the initial plan delineated in the Marie Curie proposal, and one postdoctoral student is currently actively working on the project. And the researcher didn’t finish the derived C-F bond silylation project until he finished his contract, therefore, it was not possible to do the appropriate dissemination and communication of these new results.