Bifunctional homogeneous catalysts based on first row transition metals in asymmetric hydrogenation

Agbossou‐Niedercorn, Francine; Michon, Christophe

doi:10.1016/j.ccr.2020.213523

Cited by 48 publications

(24 citation statements)

References 145 publications

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“…However, the activity and stability of such catalysts based on first row TMs remains a challenge. Therefore, the development and optimization of catalysts based on 3d transition metals is an active and highly sought after area of research [10–12] . Manganese is particularly attractive as the active metal in such catalysts in view of its high biocompatibility, which is of interest for industries in the food or pharmaceutical sector.…”

Section: Introductionmentioning

confidence: 99%

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Krieger

Sinha

Kalikadien

et al. 2021

Zeitschrift anorg allge chemie

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Reversible dissociation of H−X bond (M−L+H−X→M(X)‐L(H); ΔGHX ) is an important step during pre‐activation, catalysis and possible deactivation of acid‐base cooperative pincer based transition metal catalysts (M−L). Herein we carried out a high‐throughput computational investigation of the thermodynamic stability of different adducts in various functionalized Mn(I) based pincer complexes. We used a combination of density functional theory (DFT) and density functional tight binding (DFTB) calculations to analyze ΔGHX of >700 (M(X)‐L(H)) intermediates based on functionalized variants of four pincer type ligand scaffolds derived from PCP, CNC, PNP and SNS ligands. We discovered linear scaling relations between ΔGHX of various species. Strongest correlations were found between species of similar size and chemical nature e. g. ΔGtBuOH correlated best with ΔGiPrOH and worst with ΔGHBr . Such scaling relations can be useful for property based screening of catalysts and selection of (co)solvent/substrate/base for optimized reaction conditions. We also investigated the influence of the ligand backbone and the functionalization of donor and backbone sites in the ligand. Our analysis reveals the crucial role of the second coordination sphere functionalization for the reactivity of the complexes with impact in some cases exceeding that of the variation of the functional groups directly attached to the donor atoms.

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Section: Introductionmentioning

confidence: 99%

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Krieger

Sinha

Kalikadien

et al. 2021

Zeitschrift anorg allge chemie

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“…251 While new effective hydrogenation catalysts are searched out, 46 there's a growing interest in hydrogenation catalysts based on abundant metals due to economic, environmental and societal issues. [251][252][253] Several examples of bifunctional catalysts have already been reported in this field and others will surely appear in the future. Finally, the development of highly active catalysts, i.e.…”

Section: Discussionmentioning

confidence: 99%

Bifunctional Homogeneous Catalysts Based on Ruthenium, Rhodium and Iridium in Asymmetric Hydrogenation

Michon

Agbossou‐Niedercorn

2022

Series on Chemistry, Energy and the Environment

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“…Of these, chiral aryl alkyl alcohols are one important class of alcohols. The ubiquity of aryl alkyl alcohols as high-ranking intermediates makes them appealing precursors [8][9][10]. Thus, the invention of methods for the preparing of such chiral aryl alkyl alcohols features an important role in organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

Ru-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes via P-Chiral Monophosphorous Ligands

et al. 2022

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Chiral alcohols are among the most widely applied in fine chemicals, pharmaceuticals and agrochemicals. Herein, the Ru-monophosphine catalyst formed in situ was found to promote an enantioselective addition of aliphatic aldehydes with arylboronic acids, delivering the chiral alcohols in excellent yields and enantioselectivities and exhibiting a broad scope of aliphatic aldehydes and arylboronic acids. The enantioselectivities are highly dependent on the monophosphorous ligands. The utility of this asymmetric synthetic method was showcased by a large-scale transformation.

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Bifunctional homogeneous catalysts based on first row transition metals in asymmetric hydrogenation

Cited by 48 publications

References 145 publications

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Metal‐ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Bifunctional Homogeneous Catalysts Based on Ruthenium, Rhodium and Iridium in Asymmetric Hydrogenation

Ru-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes via P-Chiral Monophosphorous Ligands

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