Diastereoselective Photooxidation and Reduction of Chiral Iridium(III) Complexes

This is the authors' abstract. We don't add key points for this paper.

A diastereoselective photooxidation of α-amino acid (AA) complexes into imino acid complexes using a chiral iridium(III) complex as a photosensitizer and stereo-controller under visible light irradiation and oxygen was developed. It was found that the oxidative rate of Δ-[Ir(pq) 2 ( L -AA)] (pq is 2-phenylquinoline) diastereomer is significantly higher than that of the corresponding Δ-[Ir(pq) 2 ( D -AA)] diastereomer, providing a new protocol for kinetic resolution of AAs via a nonenzymatic pathway. Moreover, the thermodynamic controlled strategy offered a complemental method for the diastereoselective hydrogenation of imine bonds using NaBH 4 as a reductant under the chiral Ir(III) complex as a stereo-controller. The combination of diastereoselective photooxidation and reduction processes results in a new protocol for deracemization of α-amino acids under mild conditions. Mechanism study strongly indicates that singlet oxygen is a key participant in the reaction and the α-C–H bond cleavage of AAs is the rate-determining step.