Difunctionalizations of ? C-C bonds by Dual Nickel/Photoredox catalyzis – DiFonNiCC

The goal of this project is to develop and understand novel transition metal catalyzed sigma C-C bonds difunctionalizations to address a major scientific challenge: the rapid access to densely substituted scaffolds from readily available building blocks. To do so, we propose to implement a nickel/photoredox dual catalysis strategy. This strategy will permit to overcome the restrictions currently plaguing the field of sigma C-C bond functionalization through the exploitation of various single electron transfer mechanisms. More specifically, this strategy will allow the selective sequential functionalization of the substrates by two different agents. We will demonstrate the viability of this approach using two model reactions based on the difunctionalization of 3-membered rings (cyclopropenones and N-(Acyl)-aminocyclopropanes) by a radical source and a terminal electrophile, thus giving access to enones and chiral amines.
Moreover, to ensure the wide application of our difunctionalization strategy, it will be of paramount importance to identify the key parameters governing each elementary step. Therefore, a pivotal aspect of this project will be in-depth mechanistic study of each step of the envisioned process, with the goal of providing hands-on tools to understand and rationalize the reactivity in these systems. We plan to accomplish this by isolation of a number of key intermediates, followed by study of their reactivity using in-situ spectroscopic techniques including NMR, IR and UV-Vis spectroscopy.
The fundamental knowledge that will be uncovered in this project, backed up with relevant synthetic examples, should significantly energised the field of sigma C-C functionalization and promote both academic and industrial applications.