Deactivation mechanisms of iodo-iridium catalysts in chiral amine racemization

• DOI: 10.1016/j.tet.2020.131823
• Publication Date: 2020-12-03T06:54:52Z
• Authors: Maria H.T. Kwan; Nisha P.B. Pokar; Catherine Good; Martin F. Jones; Rachel Munday; Thomas Screen; A. John Blacker
• Keywords: 01 natural sciences; 0104 chemical sciences

The homogenous, [IrCp*I2]2, SCRAM catalyst (1) is active in the racemization of chiral amines. NMR, kinetic and structural mechanistic studies have determined the cause of catalyst deactivation to occur when ammonia or methylamine are liberated by hydrolysis or aminolysis of the intermediate imine, which tightly coordinate to the iridium centre to block turnover. Control of moisture and substrate concentration can suppress deactivation, whilst partial reactivation of spent catalyst was identified using hydroiodic acid.