Diastereoselective Photooxidation and Reduction of Chiral Iridium(III) Complexes.
Inorg Chem
; 58(1): 785-793, 2019 Jan 07.
Article
em En
| MEDLINE
| ID: mdl-30550266
ABSTRACT
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 NaBH4 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.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
China