Asymmetric Hydrogenation of 1-aryl substituted-3,4-Dihydroisoquinolines with Iridium Catalysts Bearing Different Phosphorus-Based Ligands

Abstract

Starting from the chiral 5,6,7,8-tetrahydroquinolin-8-ol core, a series of amino-phosphorus-based ligands was realized. The so-obtained amino-phosphine ligand (L1), amino-phosphinite (L2) and amino-phosphite (L3) were evaluated in iridium complexes together with the heterobiaryl diphosphines tetraMe-BITIOP (L4), Diophep (L5) and L6 and L7 ligands, characterized by mixed chirality. Their catalytic performance in the asymmetric hydrogenation (AH) of the model substrate 6,7-dimethoxy-1-phenyl-3,4-dihydroisoquinoline 1a led us to identify Ir-L4 and Ir-L5 catalysts as the most effective. The application of these catalytic systems to a library of differently substituted 1-aryl-3,4-dihydroisoquinolines afforded the corresponding products with variable enantioselective levels. The 4-nitrophenyl derivative 3b was obtained in a complete conversion and with an excellent 94% e.e. using Ir-L4, and a good 76% e.e. was achieved in the reduction of 2-nitrophenyl derivative 6a using Ir-L5.

Keywords

• atropoisomeric chirality
• chiral diphosphines
• amino phosphine
• imines reduction
• iridium complexes