Carbene-catalyzed super-reductions through direct photoactivation of intermediates – CASPI

The ultimate goal of the CASPI project is the rational design of extremely-reductive processes with N-Heterocyclic Carbene (NHC) organocatalysis through direct light-activation of already reductive catalytic intermediates.
The proposal is based on the emerging concepts, such as ConPET (Consecutive Photo-induced Electron Transfer), in which a first transformation of a photocatalyst yields a radical anion, which, in turn, could promote extreme photoreductions, as well as paradigm-shifting preliminary results.
NHC radical catalysis and extreme reductive photocatalysis are hot and highly competitive areas of research. Most of the international competition focus on methological “black-box” optimizations and have reached stalemates due to the difficulty to assess elusive intermediates and complex photophysical situations. In marked contrast, CASPI capitalizes on the experience of the consortium in handling, studying and understanding reactive NHC-based intermediates. The consortium intends i) to develop NHC patterns inducing redox activity, radical stability and strong absorptions ; ii) to perform a complete photo-electrochemical study and assessment of the photoreactivity of the key intermediates; iii) to design on this basis powerful photoNHC-catalyzed reactions involving highly reductive (Birch-type), yet selective, activations.