Quinaphos and Dihydro-Quinaphos phosphine-phosphoramidite ligands for asymmetric hydrogenation.

New derivatives of the Quinaphos ligands and the related Dihydro-Quinaphos ligands based on the more flexible 1,2,3,4-tetrahydroquinoline backbone have been prepared and fully characterised. A general and straightforward separation protocol was devised, which allowed for the gram-scale isolation of the R-a,S-c, and S-a,R-c, diastereomers. These new phosphine phosphoramidite ligands have been applied in the Rh-catalysed asymmetric hydrogenation of functionalised olefins with the achievement of excellent enantioselectivities (>= 99%) in most cases and turnover frequency (TOF) values of up to >= 20000 h(-1). These results substantiate the practical utility of readily accessible Quinaphostype ligands, which belong to the most active and selective category of ligands for Rh-catalysed hydrogenation known to date.