A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides DOI Creative Commons
Maite Molins Colomer, Javier Fernández-García, Xavier Berzosa

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер unknown

Опубликована: Дек. 8, 2024

Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past Ullmann-type reactions starting from aryl iodides. However, no procedures described activation of less reactive bromides. In this work, we successfully developed a method hydroxylation bromides promoted by copper reactor. Notably, presence both diamine ligand DMF is key reaction to proceed. An inorganic base such as Na2CO3 also improved yield minimizing formation side products. The setup has applied range disubstituted moderate good yields was tested under 24 h continuous operation, showing stable yields, thus proving robustness catalysis. Finally, lifetime reactor operating conditions calculated first time, that technology safe operate at industrial scale.

Язык: Английский

Improving the Chemical Utilization Efficiency of Pd Hydrodechlorination Catalysts through Hydrogen-Spillover Empowered Synergy between Pd and TiNiN Support DOI
Wenxuan Wang, Xiaoling Zhang, Ran Wei

и другие.

Environmental Science & Technology, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

The sustainable and affordable environmental application of Pd catalysis needs further improvement mass activity. Besides the well-recognized importance physical utilization efficiency─the ratio surface atoms forming reactant-accessible reactive sites─a lesser-known fact is that congestion these sites, which we term as chemical efficiency, also influences Herein, by leveraging 100% efficiency a fully exposed cluster (Pdn) hydrogenation activity TiNiN, developed Pdn/TiNiN high catalyst. During catalytic hydrodechlorination 4-chlorophenol subsequent phenol, Pdn focuses on H2 dissociation C–Cl cleavage, while TiNiN facilitates phenol into less toxic cyclohexanone via H-spillover. This synergy results in 20–40-fold increase rate. enhanced informs design microspheres for conversion halogenated organics from pharmaceutical wastewater fixed-bed reactor to transfer trace amounts 4-CP river water. Ultimately, this approach decentralizes use reduction processes.

Язык: Английский

Процитировано

2
(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones DOI
Hong Chen, Weiwei Zuo

Organometallics, Год журнала: 2024, Номер 43(6), С. 665 - 676

Опубликована: Март 6, 2024

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

Язык: Английский

Процитировано

1
Room Temperature Ni‐Catalyzed Ullmann Reaction of (Hetero)aryl / Vinyl Chlorides Enabled by Silylchloride‐Activated Mn Powders DOI
Minling Xü, Shigang Wu, Gang Zou

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(39)

Опубликована: Июль 24, 2024

Abstract 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 proved to be rather small. High regioselectivity could achieved between ortho ‐Cl para ‐Cl/Br halides benefiting the large effects. double‐face role TMSCl, i. e. activation but deactivation nickel catalyst, was although TMSCl‐activated appeared privileged metallic reductant. Applications protocol have been demonstrated a multigram synthesis Daclatasvir.

Язык: Английский

Процитировано

0
A Tribute to Ullmann’s Work: Expanding Copper Coil Reactor Applications toward the Hydroxylation of Aryl Bromides DOI Creative Commons
Maite Molins Colomer, Javier Fernández-García, Xavier Berzosa

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер unknown

Опубликована: Дек. 8, 2024

Copper coil flow reactors represent an economic, abundant, and durable platform for conducting copper-catalyzed reactions. These have been used in the past Ullmann-type reactions starting from aryl iodides. However, no procedures described activation of less reactive bromides. In this work, we successfully developed a method hydroxylation bromides promoted by copper reactor. Notably, presence both diamine ligand DMF is key reaction to proceed. An inorganic base such as Na2CO3 also improved yield minimizing formation side products. The setup has applied range disubstituted moderate good yields was tested under 24 h continuous operation, showing stable yields, thus proving robustness catalysis. Finally, lifetime reactor operating conditions calculated first time, that technology safe operate at industrial scale.

Язык: Английский

Процитировано

0