Mechanistic insights into asymmetric transfer hydrogenation of pyruvic acid catalysed by chiral osmium complexes with formic acid assisted proton transfer

2019 ◽  
Vol 55 (65) ◽  
pp. 9633-9636 ◽  
Author(s):  
Wan Wang ◽  
Xinzheng Yang
Keyword(s):  
Density Functional Theory ◽  
Formic Acid ◽  
Pyruvic Acid ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Transfer Hydrogenation ◽  
Asymmetric Transfer Hydrogenation ◽  
Functional Theory ◽  
Osmium Complexes ◽  
Acid Catalyzed

Density functional theory calculations reveal a proton-coupled hydride transfer mechanism with the participation of formic acid for asymmetric transfer hydrogenation of pyruvic acid catalyzed by chiral Os complexes.

scholarly journals Computational Design of SCS Nickel Pincer Complexes for the Asymmetric Transfer Hydrogenation of 1-Acetonaphthone

Catalysts ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 101 ◽  
Author(s):  
Bing Qiu ◽  
Wan Wang ◽  
Xinzheng Yang
Keyword(s):  
Density Functional ◽  
Enantiomeric Excess ◽  
Density Functional Theory Calculations ◽  
Computational Design ◽  
Transfer Hydrogenation ◽  
Pincer Complexes ◽  
Free Energy Barrier ◽  
Asymmetric Transfer Hydrogenation ◽  
Functional Theory ◽  
Prochiral Ketones

Inspired by the active site structures of lactate racemase and recently reported sulphur–carbon–sulphur (SCS) nickel pincer complexes, a series of scorpion-like SCS nickel pincer complexes with an imidazole tail and asymmetric claws was proposed and examined computationally as potential catalysts for the asymmetric transfer hydrogenation of 1-acetonaphthone. Density functional theory calculations reveal a proton-coupled hydride transfer mechanism for the dehydrogenation of (R)-(+)-1-phenyl-ethanol and the hydrogenation of 1-acetonaphthone to produce (R)-(+)-1-(2-naphthyl)ethanol and (S)-(−)-1-(2-naphthyl)ethanol. Among all proposed Ni complexes, 1Ph is the most active one with a rather low free energy barrier of 24 kcal/mol and high enantioselectivity of near 99% enantiomeric excess (ee) for the hydrogenation of prochiral ketones to chiral alcohols.

scholarly journals Theoretical study of the oxidation of formic acid on a PtPd(111) surface

2019 ◽  
Vol 44 (1) ◽  
pp. 67-73 ◽  
Author(s):  
Ying-Ying Wang
Keyword(s):  
Density Functional Theory ◽  
Formic Acid ◽  
Density Functional ◽  
Main Product ◽  
Theoretical Study ◽  
Reaction Pathway ◽  
Density Functional Theory Calculations ◽  
Acid Decomposition ◽  
Functional Theory ◽  
Formic Acid Decomposition

By performing density functional theory calculations, the adsorption configurations of formic acid and possible reaction pathway for HCOOH oxidation on PtPd(111) surface are located. Results show that CO2 is preferentially formed as the main product of the catalytic oxidation of formic acid. The formation of CO on the pure Pd surface could not possibly occur during formic acid decomposition on the PtPd(111) surface owing to the high reaction barrier. Therefore, no poisoning of catalyst would occur on the PtPd(111) surface. Our results indicate that the significantly increased catalytic activity of bimetallic PtPd catalyst towards HCOOH oxidation should be attributed to the reduction in poisoning by CO.

A Phosphine-Free Mn(I)-NNS Catalyst For Asymmetric Transfer Hydrogenation of Acetophenone: A Theoretical Prediction

2021 ◽  
Author(s):  
Yaqi Zhao ◽  
Lin Zhang ◽  
Min Pu ◽  
Ming Lei
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Theoretical Prediction ◽  
Density Functional ◽  
Dft Method ◽  
Transfer Hydrogenation ◽  
Asymmetric Transfer Hydrogenation ◽  
Functional Theory ◽  
Hydrogen Activation

A density functional theory (DFT) method was employed to investigate the reaction mechanism of hydrogen activation and asymmetric transfer hydrogenation (ATH) of acetophenone catalyzed by well-defined phosphine-free Mn(I)-NNS complex. The...

scholarly journals First-Principles Density Functional Theory Calculations for Formic Acid Adsorption onto Hydro-Garnet Compounds

ACS Omega ◽  
2020 ◽  
Vol 5 (8) ◽  
pp. 4083-4089
Author(s):  
Masanobu Nakayama ◽  
Kunihiro Ishida ◽  
Kentaro Watanabe ◽  
Naoto Tanibata ◽  
Hayami Takeda ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Formic Acid ◽  
First Principles ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Functional Theory

scholarly journals Computational Prediction of Chiral Iron Complexes for Asymmetric Transfer Hydrogenation of Pyruvic Acid to Lactic Acid

Molecules ◽  
2020 ◽  
Vol 25 (8) ◽  
pp. 1892
Author(s):  
Wan Wang ◽  
Xinzheng Yang
Keyword(s):  
Free Energy ◽  
Formic Acid ◽  
Pyruvic Acid ◽  
Energy Barrier ◽  
Density Functional ◽  
Iron Complexes ◽  
Computational Prediction ◽  
Transfer Hydrogenation ◽  
Free Energy Barrier ◽  
Asymmetric Transfer Hydrogenation

Density functional theory calculations reveal a formic acid-assisted proton transfer mechanism for asymmetric transfer hydrogenation of pyruvic acid catalyzed by a chiral Fe complex, FeH[(R,R)-BESNCH(Ph)CH(Ph)NH2](η6-p-cymene), with formic acid as the hydrogen provider. The rate-determining step is the hydride transfer from formate anion to Fe for the formation and dissociation of CO2 with a total free energy barrier of 28.0 kcal mol−1. A series of new bifunctional iron complexes with η6-p-cymene replaced by different arene and sulfonyl groups were built and computationally screened as potential catalysts. Among the proposed complexes, we found 1g with η6-p-cymene replaced by 4-isopropyl biphenyl had the lowest free energy barrier of 26.2 kcal mol−1 and excellent chiral selectivity of 98.5% ee.

Sign in / Sign up

Export Citation Format

Share Document