Synthesis, Characterization, and Reactivity of Ruthenium Bis-Allyl Complexes with Chiral Phosphine-Phosphite Ligands
摘要:
A series of ruthenium bis-allyl complexes of formula Ru(eta(3)-2-MeC3H4)(2)(P-OP) (I) which incorporate chiral phosphine-phosphite ligands (P-OP) have been prepared and characterized. Compounds I exist in solution as a mixture of two diastereomers (maj and min) differing in the configuration at the metal. Both isomers are in equilibrium in solution, and their ratio varies with the nature of the P-OP ligand. Along the series, higher values of the maj/min ratio were observed with complexes bearing less sterically encumbered phosphite groups. In reactions of compounds I with protic reagents removal of one or two ally! ligands has been observed. Thus, reaction of 1h with pentachlorophenol produces the mixed allyl-phenoxide 3h, whereas reaction of la or 1h with tiglic acid produces the corresponding tiglates 4a,h, respectively. In addition, compounds I generate active catalysts for the hydrogenation of tiglic and 2-methyl-2-pentenoic acids. By appropriate optimization of the structure of the P-OP ligand, enantioselectivities up to 89% ee were obtained in these reactions. In addition, complexes I also catalyze the ROMP reaction of norbornene, although low initiation rates have been observed for this process.
Synthesis, Characterization, and Reactivity of Ruthenium Bis-Allyl Complexes with Chiral Phosphine-Phosphite Ligands
摘要:
A series of ruthenium bis-allyl complexes of formula Ru(eta(3)-2-MeC3H4)(2)(P-OP) (I) which incorporate chiral phosphine-phosphite ligands (P-OP) have been prepared and characterized. Compounds I exist in solution as a mixture of two diastereomers (maj and min) differing in the configuration at the metal. Both isomers are in equilibrium in solution, and their ratio varies with the nature of the P-OP ligand. Along the series, higher values of the maj/min ratio were observed with complexes bearing less sterically encumbered phosphite groups. In reactions of compounds I with protic reagents removal of one or two ally! ligands has been observed. Thus, reaction of 1h with pentachlorophenol produces the mixed allyl-phenoxide 3h, whereas reaction of la or 1h with tiglic acid produces the corresponding tiglates 4a,h, respectively. In addition, compounds I generate active catalysts for the hydrogenation of tiglic and 2-methyl-2-pentenoic acids. By appropriate optimization of the structure of the P-OP ligand, enantioselectivities up to 89% ee were obtained in these reactions. In addition, complexes I also catalyze the ROMP reaction of norbornene, although low initiation rates have been observed for this process.
Mildly does it: A highlyenantioselective catalyst for the hydrogenation of N‐aryl imines is described (see scheme). This catalyst offers practical advantages because it operates under very mild conditions and is based on an Ru complex with a diamine as the sole chiral ligand.