Reduction asymetrique catalysee par des complexes de metaux de transition IV. synthese d'amines chirales au moyen d'un complexe de rhodium et d'isopropylidene dihydroxy-2,3 bis(diphenylphosphino)-1,4 butane (diop)

Rhodium

“…The first report on enantioselective homogeneous reduction of C=N double bonds mediated by rhodium complexes appeared in 1975. Kagan et al reported that N-benzyl-a-phenyl ethylamine was prepared by hydrosilylation with 65% optical purity, using a chiral rhodium complex with (+)-DIOP [63]. Some years later, the Markó group reported that using catalysts prepared in situ from [RhCl(NBD)] 2 and chiral phosphines of the type Ph 2 PCHRCH 2 PPh 2 (R = Ph, iPr, PhCH 2 ), optical yields up to 77% were achieved, although reproducibility of the results was poor [64].…”

The Chiral Switch of (S)-Metolachlor: A Personal Account of an Industrial Odyssey in Asymmetric Catalysis

“…[16] In contrast, the enantioselective catalytic reduction of CN functions was practically unknown. The best results were reported for the hydrosilylation of some N-alkylimines with ee×s up to 65% [17] while the best ee for hydrogenation was only 22%. [6] The reduction of N-arylimines had never been described.…”

Iridium(I)‐Catalysed Tandem Hydrosilylation‐Protodesilylation of Imines

“…[1] Hydrosilylation of imines, in which the Si-H bond is added across the C=N bond, is an attractive alternative approach to the hydrogenation of imines as it is experimentally simple, does not require high pressure or temperature, and makes use of readily available silanes. Most of the effective catalysts for imine hydrosilylation are transition metal complexes, using metals including Rh, [2][3][4] Ru, [5,6] Ti, [7,8] Cu, [9] and Ni [10] however a recent report, using high throughput screening methods, also identified a number of new Sn and Zn catalysts. [11] There have been only limited reports of imine hydrosilylation employing complexes of Ir, [12] although Ir complexes are known to promote the hydrogenation of imines.…”