Journal ArticleDOI
Ru(arene)(amino alcohol)-Catalyzed Transfer Hydrogenation of Ketones: Mechanism and Origin of Enantioselectivity
TLDR
The mechanism of the Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones using isopropyl alcohol as the hydrogen source has been studied by means of hybrid density functional methods as discussed by the authors.Abstract:
The mechanism of the Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones using isopropyl alcohol as the hydrogen source has been studied by means of hybrid density functional methods (B3PW91). Three mechanistic alternatives were evaluated, and it was shown that the reaction takes place via a six-membered transition state, where a metal-bound hydride and a proton of a coordinated amine are transferred simultaneously to the ketone. Further calculations provided a general rationale for the rate of the reaction by comparison of steric effects in the ground and transition states of the ruthenium hydride complex. It was found that the TS has a strong preference for planarity, and this in turn is dependent on the conformational behavior of the O,N-linkage of the amino alcohol ligand. Finally, a general model, rationalizing the enantioselectivity of the reaction, was developed. Experimental studies of both rate and enantioselectivity were used in order to support the computational results.read more
Citations
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Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo‐ and Stereoselective Hydrogenation of Ketones
Ryoji Noyori,Takeshi Ohkuma +1 more
TL;DR: The newly devised [RuCl(2)(phosphane)(2)(1,2-diamine)] complexes are excellent precatalysts for homogeneous hydrogenation of simple ketones which lack any functionality capable of interacting with the metal center.
Journal ArticleDOI
Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes
TL;DR: In this article, the authors classified the catalytic cycles for the H2-hydrogenation (H) and transfer hydrogenation (T) of CO and cN bonds catalyzed by over 100 ruthenium hydride complexes in organic and aqueous media.
Journal ArticleDOI
Mechanistic aspects of transition metal-catalyzed hydrogen transfer reactions.
TL;DR: In this tutorial review recent mechanistic studies on transition metal-catalyzed hydrogen transfer reactions are discussed and an important question is whether the substrate coordinates to the metal (inner-sphere hydrogen transfer) or if there is a direct concerted transfer of hydrogen from the metal to substrate (outer-spheres hydrogen transfer).
Journal ArticleDOI
The Metal−Ligand Bifunctional Catalysis: A Theoretical Study on the Ruthenium(II)-Catalyzed Hydrogen Transfer between Alcohols and Carbonyl Compounds
TL;DR: The ternary system consisting of [RuCl2(η6-benzene)]2, N-tosylethylenediamine or ethanolamine, and KOH (Ru:amine:KOH = 1:1:2 molar ratio) catalyzes reversible hydrogen transfer between alcohols and carbonyl compounds.
Journal ArticleDOI
Supported chiral catalysts on inorganic materials
Choong Eui Song,Sang‐gi Lee +1 more
References
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Density‐functional thermochemistry. III. The role of exact exchange
TL;DR: In this article, a semi-empirical exchange correlation functional with local spin density, gradient, and exact exchange terms was proposed. But this functional performed significantly better than previous functionals with gradient corrections only, and fits experimental atomization energies with an impressively small average absolute deviation of 2.4 kcal/mol.
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Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
P. Jeffrey Hay,Willard R. Wadt +1 more
TL;DR: In this article, effective core potentials (ECP) have been derived to replace the innermost core electron for third row (K), fourth row (Rb-Ag), and fifth row (Cs-Au) atoms.
Journal ArticleDOI
Energy-adjustedab initio pseudopotentials for the second and third row transition elements
TL;DR: In this paper, nonrelativistic and quasirelativisticab initio pseudopotentials substituting the M(Z−28)+-core orbitals of the second row transition elements and the M (Z−60)+- core orbitals, respectively, and optimized (8s7p6d)/[6s5p3d]-GTO valence basis sets for use in molecular calculations were generated.
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Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent
Jacopo Tomasi,Maurizio Persico +1 more