Robbe Grauls

Based on the excellent photocatalytic ability of porphyrin and the chiral advantage of amino acids, porphyrin has been modified using amino acids. The porphyrin–amino acids can exhibit opposite trends in enantioselectivity in the photocatalytic oxidation of tyrosine reaction. Moreover, the porphyrin–phenylalanine derivatives with carboxyl-terminal groups catalyze 700.10% more dityrosine in d-type substrates than in l-type substrates.

Porphyrin-based nanomaterials have attracted much attention in photocatalysis due to their excellent photoelectrocatalytic ability and strong intermolecular interaction forces. Herein, a series of chiral assemblies of porphyrin–amino acid derivatives are prepared by linking different types of amino acids with terminal modifications to tetrakis(4-carboxyphenyl)porphyrin via covalent bonding and their catalytic ability in enantioselective photocatalytic oxidation of tyrosine is investigated. The results show that the amino acid type and terminal groups significantly affect the macroscopic assembly morphology and microscopic chiral space of the porphyrin–amino acid derivatives, which is consistent with the results of molecular dynamics simulations and further impacts the rate and enantioselectivity of tyrosine chiral photocatalytic oxidation. These results provide new avenues for applying porphyrin derivatives in chiral photocatalysis.