Asymmetric hydrogenation with highly active IndolPhos-Rh catalysts: kinetics and reaction mechanism

Abstract

The mechanism of the Indol- Phos–Rh-catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X-ray crystal structure determination, kinetic measurements, high-pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis– Menten kinetics. A large value of KM (KM=5.01 0.16m) is obtained, which indicates that the Rh–solvate complex is the catalyst resting state, which has been observed by high-pressure NMR spectroscopy. DFT calculations on the substrate–catalyst complexes, which are undetectable by experimental means, suggest that the major substrate–catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism of asymmetric hydrogenation reactions with C1-symmetric heteroditopic and monodentate ligands.