Pd/bisphosphines complexes are highly effective catalysts for asymmetric hydrogenation of activated imines in trifluoroethanol. The asymmetric hydrogenation of N-diphenylphosphinyl ketimines 3 with Pd(CF3CO2)/(S)-SegPhos indicated 87-99% ee, and N-tosylimines 5 could gave 88-97% ee with Pd(CF3CO2)/(S)-SynPhos as a catalyst. Cyclic N-sulfonylimines 7 and 11 were hydrogenated to afford the useful...

DFT computations of various possible reaction pathways in asymmetric hydrogenation of methyl (Z-α)acetylaminocinnamate catalysed by Rh-TangPHOS complex revealed the clear preference of the dihydride pathway. This conclusion was explicitly confirmed by the structure of the monohydride intermediate intercepted in the low temperature NMR hydrogenation experiments. DFT analysis of the origin of ena...

Iridium-catalyzed asymmetric hydrogenation of N-alkyl-2-alkylpyridinium salts provided 2-aryl-substituted piperidines with high levels of enantioselectivity. Simple benzyl and other alkyl groups successfully activated the challenging pyridine substrates toward hydrogenation. The use of the unusual chiral-phosphole-based MP(2) -SEGPHOS was the key to the success of this approach which provides a...

Within the realm of catalytic asymmetric hydrogenation, the focus continues to be on the use of chiral metal complexes in conjunction with a hydrogen source. Recently, the widespread development of organocatalysis, including the invention of iminium activation, has led to the discovery of many new enantioselective transformations. Based on this strategy, a number of bioinspired processes for th...

In this paper we describe new multi-catalysis cascade (MCC) reactions for the one-pot synthesis of highly functionalized non-symmetrical malonates. These metal-free reactions are either five-step (olefination/hydrogenation/alkylation/ketenization/esterification) or six-step (olefination/hydrogenation/alkylation/ketenization/esterification/alkylation), and employ aldehydes/ketones, Meldrum's aci...

A highly regio- and enantioselective cobalt-catalyzed sequential hydrosilylation/hydrogenation of alkynes was developed to afford chiral silanes. This one-pot method is operationally simple and atom economic. It makes use of relatively simple and readily available starting materials, namely alkynes, silanes, and hydrogen gas, to construct more valuable chiral silanes. Primary mechanistic studie...

A concise and efficient total synthesis of the spermidine alkaloid (-)-isooncinotine (1) incorporating a 22-membered lactam ring is outlined. The approach is largely catalysis-based, involving a selective iron-catalyzed alkyl-aryl cross-coupling reaction of a difunctionalized pyridine substrate, a heterogeneous asymmetric hydrogenation step to set the chiral center of the target, and a highly i...

Several hydrogenation reactions involving O-debenzylations, aromatic nitro group reductions and reductive dethionations were investigated under continuous flow conditions in a novel, laboratory scale hydrogenation device that combines endogeneous hydrogen generation and heterogeneous Pd/C or Raney-Ni catalyst cartridges. The hydrogenation of organic compounds through addition and/or hydrogenoly...

In this work structural defects were created in P25-TiO2 nanoparticles by using hydrogen DC plasma treatment in different temperatures and exposure times. X-Ray diffraction measurements show that the structure of TiO2 remains unchanged after hydrogenation. Diffuse reflectance spectroscopy measurements demonstrated band gap of TiO2 was not changed considerably by the hydrogenation. However, by a...

The kinetics and reaction network of hydrodemetallation (HDM) reactions and the pattern of metal deposition have been investigated using a model residuum oil, consisting of nickel porphyrins (Nietioporphyrin (Ni-EP), Ni-tetraphenylporphyrin (Ni-TPP), and Nitetra(3-methylphenyl)porphyrin (Ni-T3MPP)) dissolved in a clean (N and S free) mineral oil. Reactions were carried out over a commercial CoO...