Mechanistic analysis of the transition metal-catalyzed hydrogenation of imines and functionalized enamines

The asymmetric hydrogenation of prochiral imines has been mainly studied on cationic rhodium or iridium complexes and involves the coordination of the nitrogen atom on the metal centre. Oxidative addition of dihydrogen followed by one hydride transfer onto the carbon atom produces a (T-bonded nitrogenmetal intermediate from which reductive elimination occurs with the second hydride to produce the amine. From all these reactivity studies we propose that in an early step a hydrogen atom transfer could occur on the nitrogen atom to generate an iminium species which coordinates the metal centre through the C = N double bond. The Shvo catalyst, an active neutral ruthenium(II) complex, presents the particularity to transfer almost simultaneously a proton from the hydroxycyclopentadienyl ligand and a hydride bonded to the metal center. In this case too, we suggest the first proton transfer generates an iminium species. Morever, a few titanium complexes have been shown to catalyze the hydrogenation of imines. Concerning enamines, literature is rather scarce on catalytic success. On the contrary, many studies focused on hydrogenation of enamides, which represent functionalized enamines, and enantiomeric excesses very close to 100% have been obtained. Extensive studies of the effect of the (chiraldiphosphine)Rh+ framework on the asymmetric induction have shown that several reversible steps can occur related to the oxidative addition of dihydrogen before or after the coordination of the enamide: the irreversible step directly connected to the asymmetric induction is the formation of the chiral alkyl-rhodium species. (C) 2009 Published by Elsevier B.V.