A combined experimental and computational study to decipher complexity in the asymmetric hydrogenation of imines with Ru catalysts bearing atropisomerizable ligands

León, Félix; Comas‐Vives, Aleix; Álvarez, Eleuterio; Pizzano, Antonio

doi:10.1039/d0cy02390f

Cited by 7 publications

(10 citation statements)

References 103 publications

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“…Furthermore, bifunctional catalysts have been reported in which a stereogenic metal center is generated upon substrate and/or reagent binding. − Moreover, Soduoka recently reported a chiral Lewis acid catalyst in which the resulting Ni(II) complex contains centrochirality after substrate binding . Pizzano published a study on Noyori-type ruthenium-catalyzed asymmetric hydrogenations of imines in which an intermediate with metal-centered chirality is involved …”

Section: Metal-centered Stereogenicity In Catalytic Intermediatesmentioning

confidence: 99%

“…277 Pizzano published a study on Noyori-type rutheniumcatalyzed asymmetric hydrogenations of imines in which an intermediate with metal-centered chirality is involved. 278 Another prominent class of chiral transition metal catalysts in which the precatalyst is often devoid of metal-centered stereogenicity, but a stereogenic metal atom is formed within the catalytic cycle are tetradentate salen, salalen, and salan complexes. Consequently, such a topology is commonly observed when a trans−cis isomerization of the tetradentate ligand results in metal centrochirality (Schemes 12 and 15).…”

Section: Metal-centered Stereogenicity In Catalytic Intermediatesmentioning

confidence: 99%

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Metal Stereogenicity in Asymmetric Transition Metal Catalysis

2023

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Chiral transition metal catalysts represent a powerful and economic tool for implementing stereocenters in organic synthesis, with the metal center providing a strong chemical activation upon its interaction with substrates or reagents, while the overall chirality of the metal complex achieves the desired stereoselectivity. Often, the overall chiral topology of the metal complex implements a stereogenic metal center, which is then involved in the origin of the asymmetric induction. This review provides a comprehensive survey of reported chiral transition metal catalysts in which the metal formally constitutes a stereocenter. A stereogenic metal center goes along with an overall chiral topology of the metal complex, regardless of whether the ligands are chiral or achiral. Implications for the catalyst design and mechanism of asymmetric induction are discussed for half-sandwich, tetracoordinated, pentacoordinated, and hexacoordinated chiral transition metal complexes containing a stereogenic metal center. The review distinguishes between chiral metal catalysts originating from the coordination to chiral ligands and those which are solely composed of optically inactive ligands (achiral or rapidly interconverting enantiomers) prior to complexation (dubbed “chiral-at-metal” catalysts).

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Section: Metal-centered Stereogenicity In Catalytic Intermediatesmentioning

confidence: 99%

Section: Metal-centered Stereogenicity In Catalytic Intermediatesmentioning

confidence: 99%

Metal Stereogenicity in Asymmetric Transition Metal Catalysis

2023

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“…To the best of our knowledge, this activation energy data showed that H 2 activation on Ru-ZrP catalyst was facile compared with the previous work. [76,77] This suggested that the interfacial RuÀ O could act as an active site for H 2 activation (RuÀ O + H 2 !H 1 À Ru + OÀ H 2 ). According to the Bader charge analysis, the H atom dissociated onto the interface O (i. e. the H 2 atom) presents a charge state of H δ + (δ = 0.62 j e j), leaving the other H 1 atom on Ru as H δÀ (δ = 0.13 j e j).…”

Section: Dft Calculationsmentioning

confidence: 99%

A Cationic Ru(II) Complex Intercalated into Zirconium Phosphate Layers Catalyzes Selective Hydrogenation via Heterolytic Hydrogen Activation

Chen

Xia

et al. 2021

ChemCatChem

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Catalytic hydrogenations constitute economic and clean transformations to produce pharmaceutical and a multitude of fine chemicals in chemical industry. Herein, we report a cationic Ru(II) complex intercalated into zirconium phosphate (ZrP) layers that enables the efficient catalytic conversion of furfural and other biomass-derived carbonyl compounds into the corresponding alcohols through selective hydrogenation of C=O group. The ZrP layers acted not only as a support for the Ru-complex, but also as the new ligands to tune the Ru(II) center via forming RuÀ O bond. The resulting catalysts exhibit excellent catalytic performance and can be easily recycled for six times without significant loss of activity and selectivity. The Ru(II) complex-intercalated catalysts have been characterized by XRD, SEM, HRTEM, HAADF-STEM, XPS, FT-IR, DR-UV/Vis, EXAFS and XANES. Especially, it is observed that the appropriate interlayer spacing between ZrP layers is favorable to stabilize the Ru(II) complex. Notably, on the basis of the further characterization and density functional theory (DFT) calculation, it is identified that the interaction of cationic Ru(II) complex and PÀ OH group within ZrP layers leads to the high catalytic performance in selective hydrogenation, and the newly formed RuÀ OÀ P species plays a crucial role in the heterolytic hydrogen activation and selective hydrogenation of biomass-derived compounds containing a carbonyl group.

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“…Several efficient enantioselective Mn(I)‐based reduction catalysts have been reported [8,9,37] . Transfer hydrogenation by acid‐base cooperative catalysts has been investigated both computationally and experimentally [38–48] . Evidence has been presented for both an inner‐ and outer‐sphere pathways [49,50] …”

Section: Introductionmentioning

confidence: 99%

“…[ 8 , 9 , 37 ] Transfer hydrogenation by acid‐base cooperative catalysts has been investigated both computationally and experimentally. [ 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ] Evidence has been presented for both an inner‐ and outer‐sphere pathways. [ 49 , 50 ]…”

Section: Introductionmentioning

confidence: 99%

The Impact of Computational Uncertainties on the Enantioselectivity Predictions: A Microkinetic Modeling of Ketone Transfer Hydrogenation with a Noyori‐type Mn‐diamine Catalyst

Krieger

Pidko

2021

ChemCatChem

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Selectivity control is one of the most important functions of a catalyst. In asymmetric catalysis the enantiomeric excess (e.e.) is a property of major interest, with a lot of effort dedicated to developing the most enantioselective catalyst, understanding the origin of selectivity, and predicting stereoselectivity. Herein, we investigate the relationship between predicted selectivity and the uncertainties in the computed energetics of the catalytic reaction mechanism obtained by DFT calculations in a case study of catalytic asymmetric transfer hydrogenation (ATH) of ketones with an Mn‐diamine catalyst. Data obtained from our analysis of DFT data by microkinetic modeling is compared to results from experiment. We discuss the limitations of the conventional reductionist approach of e.e. estimation from assessing the enantiodetermining steps only. Our analysis shows that the energetics of other reaction steps in the reaction mechanism have a substantial impact on the predicted reaction selectivity. The uncertainty of DFT calculations within the commonly accepted energy ranges of chemical accuracy may reverse the predicted e.e. with the non‐enantiodetermining steps contributing to e.e. deviations of up to 25 %.

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A combined experimental and computational study to decipher complexity in the asymmetric hydrogenation of imines with Ru catalysts bearing atropisomerizable ligands

Abstract: RuCl2(P–OP)(N–N) complexes containing an atropisomerizable phosphine–phosphite and a chiral diamine are effective catalyst precursors for the asymmetric hydrogenation of N-aryl imines following an outer-sphere mechanism.

Cited by 7 publications

References 103 publications

Metal Stereogenicity in Asymmetric Transition Metal Catalysis

Metal Stereogenicity in Asymmetric Transition Metal Catalysis

A Cationic Ru(II) Complex Intercalated into Zirconium Phosphate Layers Catalyzes Selective Hydrogenation via Heterolytic Hydrogen Activation

The Impact of Computational Uncertainties on the Enantioselectivity Predictions: A Microkinetic Modeling of Ketone Transfer Hydrogenation with a Noyori‐type Mn‐diamine Catalyst

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