Atroposelective synthesis of heterobiaryls using supramolecular photoredox organocatalysts – AtropoPhotoCat

Atropoisomers are an important class of chiral molecules whose enantioselective synthesis often represents a challenge and require the development of efficient original, highly selective, and environmentally-friendly reactions. The present project is in this vein, by proposing a supramolecular approach of metal-free photocatalyzed reactions, for the enantioselective synthesis of heterobiaryl atropisomers, in the confined space of chiral molecular cages. The objectives of this project are: 1) the efficient preparation of a wide scope of heterobiaryl class-3 atropisomers of medicinal interest; 2) the design and synthesis of enantiopure molecular receptors of different sizes and shapes and chirality and incorporating a metal-free porphyrin, as a visible light photoredox catalyst; 3) experimental and theoretical studies of the selected reactions and their mechanisms, to optimize the design of the 3D supramolecular organocatalysts. Chiral covalent cages (cyclotri- or tetra-veratrylene, cavitand) with a metal-free porphyrin as visible light-activated photocatalytic site will be synthesized and tested on arylations. The synergy arising from the cage-reactants interactions, and the photoredox catalyst within the cage structure, should lead to high yields and enantiomeric excesses.
In this project four partners with complementary skills in synthesis, photoinduced reactions, chirality, molecular cages, supramolecular catalysis and in computational studies are involved.