Theoretical Studies On Hydrogenation Of Ketones Catalyzed By Transition Metal And Mechanism Of Aldehyde And Ketone Hydroacylation Catalyzed By MOCC

Since the 1990s, Japanese scientists Noyori and co-works developed Ru-diphosphine-diamine catalyst. No matter in industrial production or synthesis of organic compound, the hydrogenation of ketones reactions catalyzed by this catalysts have been widely used. Aldehydes and ketones hydroacylation reactions have attracted a lot of attention, because activation of C-H bond of aldehydes and C-C bond activation of ketones via this reaction can yield ketones, and some of them are very important organic compound, such as natural products, and so forth. Jun and co-workers who employed a cataylst contains a Wilkinson's catalyst and an organic catalyst 2-amino-3-picoline, which can effectively active alkenes hydroacylation with aldehydes and ketones reactions and this system was named metal-organic cooperative catalysis, short for MOCC. The experimental mechanisms of aldehydes and ketones hydroacylation were proposed by them. In this work, we studied of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh3)2 in H2-hydrogenation of ketones and mechanism of intermolecular hydroacylation of aldehydes and ketone catalyzed by MOCC system in theoretical aspect. And the results are shown below: 1. Hydrogenation of ketones catalyzed by transition metalDensity functional theory (DFT) method was employed to research seven different X ligands effect on the catalytic activities of complexes RuHX(diamine)(PPh3)2 in processes of ketones hydorgenation. Studies show that a strong trans influence ligand X in catalysts show better catalytic activities than the low ones. Complexes with the ligand which could weaken Ru-H1 bond will show good activity in both hydrogen transfer and hydrogen coordination processes, but it is relatively difficult to finish hydrogen splitting steps for them and the catalysts with OMe, CCMe and H ligand show better catalytic activities in H2 hydrogenation of ketones to alcohols, these were agreement with exprimental results.2. Alkene hydroacylation with aldehyde and ketone catalyzed by MOCCUsing G03 software to study and compare the mechanism of alkene hydroacylation with aldehyde and ketone catalyzed by MOCC system both in netural and cationic system. The computational results indicated that aldehyde or ketone hydroacylation with alkene reactions, no matter in kinetics or thermodynamics aspects the cationic system pathways are more favorable than the neutral ones.