Me-AnilaPhos: a new chiral phosphine-phosphoramidite ligand for a highly efficient Rh-catalyzed asymmetric olefin hydrogenation

A cationic rhodium(I) complex with a novel chiral phosphine-phosphoramidite ligand based on 2-diphenylphosphino-N-methylaniline and R-BINOL moieties has been synthesized. The complex provided remarkably high activity and enantioselectivity in the asymmetric hydrogenation of methyl (Z)-α-acetamidocinnamate (100% conversion after 10 min, 98% ee) and dimethyl itaconate (100% conversion after 26 min, 96% ee) under ambient conditions (1 bar hydrogen pressure, room temperature) using 1 mol % of the catalyst in dichloromethane as solvent. On the other hand, when hydrogenation was performed in methanol, both conversion and enantioselectivity were significantly diminished, due to the partial decomposition of the rhodium/phosphine-phosphoramidite complex.