Recent Advances in Non-Precious Metal Catalysis

Chong, Eugene; Wu, Hao; Lee, Jaehee; Forson, Kelton; Haddad, Nizar

doi:10.1021/acs.oprd.3c00310

Cited by 4 publications

(1 citation statement)

References 119 publications

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“…Recently, some nickel catalysts , exhibited high activities and enantioselectivities in synthesizing compounds with chiral C–N bonds via reductive aminations of ketones. − However, more challenging ATH and AH reactions of ketones have been developed slowly. Despite reports of a number of hydrogenation or transfer hydrogenation reactions of ketones catalyzed by nickel complexes, most of them are not asymmetric. ,− To the best of our knowledge, , there are only three examples of nickel-catalyzed ATH reactions of ketones to date.…”

Section: Introductionmentioning

confidence: 99%

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

Chen,

Zuo

2024

Organometallics

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Asymmetric transfer hydrogenation (ATH) of ketones is an efficient method for constructing chiral alcohols that are widely used in synthesizing various fine chemicals. Currently, most of the existing catalysts contain precious metals that are highly toxic and scarce, which limits industrial application and sustainability. Therefore, the development of catalysts based on earth-abundant and environmentally friendly 3d metals is an important research topic. We previously reported that amidoene(amido)diphosphine Ni(II) catalysts exhibited promising reactivities. However, the enantioselectivity of the catalytic system was not satisfactory. Here, we report (primary amido)-ene(amido)-Ni(II)diphosphine catalyst 2n containing a P-chirogenic substituted ferrocene moiety in the ligand backbone and its analogue (2m). 2n was used for ATHs of a range of ketones with improved enantioselectivity, affording secondary alcohols of the (S)configuration with up to 98% enantiomeric excess (e.e.). Computational results indicated that in the reaction system of catalyst 2n, the (S)-configuration of the phosphine kept the (S)-planar chiral ferrocene moiety far from the reacting site in the transition state that produced the (S)-configured alcohol. This created space for the aryl ring of the substrate and the ene(amido) moiety of the catalyst to approach each other and form a strong π−π interaction that enhanced the enantioselectivity.

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Section: Introductionmentioning

confidence: 99%

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

Chen,

Zuo

2024

Organometallics

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Room Temperature Ni‐Catalyzed Ullmann Reaction of (Hetero)aryl/Vinyl Chlorides Enabled by Silylchloride‐Activated Mn Powders

Xü,

Wu,

Zou

2024

Eur J Org Chem

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A room temperature Ni‐catalyzed, Mn‐mediated homocoupling of (hetero)aryl and vinyl chlorides using Mn powders pre‐activated by trimethylsilylchloride (TMSCl) in DMA is reported. Large steric effects were observed while electronic influences from aryl chlorides proved to be rather small. High regioselectivity could be achieved between ortho‐Cl and para‐Cl/Br of aryl halides benefiting from the large steric effects. A double‐face role of TMSCl, i.e. activation of Mn powders but deactivation of nickel catalyst, was observed although TMSCl‐activated Mn powders appeared to be the privileged metallic reductant. Applications of the protocol have been demonstrated in a multigram synthesis of Daclatasvir.

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Improving the Chemical Utilization Efficiency of Pd Hydrodechlorination Catalysts through Hydrogen-Spillover Empowered Synergy between Pd and TiNiN Support

Wang,

Zhang,

Ran

et al. 2024

Environ. Sci. Technol.

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The sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency�the ratio of surface atoms forming reactantaccessible reactive sites�a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pd n ) and the hydrogenation activity of TiNiN, we developed Pd n / TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pd n focuses on H 2 dissociation and C−Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20−40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pd n /TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.

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Recent Advances in Non-Precious Metal Catalysis

Cited by 4 publications

References 119 publications

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

Room Temperature Ni‐Catalyzed Ullmann Reaction of (Hetero)aryl/Vinyl Chlorides Enabled by Silylchloride‐Activated Mn Powders

Improving the Chemical Utilization Efficiency of Pd Hydrodechlorination Catalysts through Hydrogen-Spillover Empowered Synergy between Pd and TiNiN Support

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