Development of Facile and Simple Processes for the Heterogeneous Pd-Catalyzed Ligand-Free Continuous-Flow Suzuki–Miyaura Coupling

Yamada, Tsuyoshi; Jiang, Jing; Ito, Naoya; Park, Kwihwan; Masuda, Hayato; Furugen, Chikara; Ishida, Moeka; Ōtori, Seiya; Sajiki, Hironao

doi:10.3390/catal10101209

Cited by 6 publications

(4 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The process started in batch with STY 0.08 gL −1 h −1 and scaled up to ∼28 gL −1 h −1 in a continuous flow system. Although the catalyst uses Pd, its loading (0.32 wt%) is lower than usually required (as much as 7 wt%) ( Cossaboon, 1980 ; Ichitsuka et al., 2019 ; Yamada et al., 2020 ) and it is reusable many times. Further, in our synthesis, ∼92% of the Pd used is retained in the catalyst.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Nitro to amine reductions using aqueous flow catalysis under ambient conditions

2021

View full text Add to dashboard Cite

Summary A catalyst based on Pd on glass wool (Pd@GW) shows exceptional performance and durability for the reduction of nitrobenzene to aniline at room temperature and ambient pressure in aqueous solutions. The reaction is performed in a flow system and completed with 100% conversion under a variety of flow rates, 2 to 100 mLmin −1 (normal laboratory fast flow conditions). Sodium borohydride or dihydrogen perform well as reducing agents. Scale-up of the reaction to flows of 100 mLmin −1 also shows high conversions and robust catalytic performance. Catalyst deactivation can be readily corrected by flowing a NaBH 4 solution. The catalytic system proves to be generally efficient, performing well with a range of nitroaromatic compounds. The shelf life of the catalyst is excellent and its reusability after 6-8 months of storage showed the same performance as for the fresh catalyst.

show abstract

Section: Resultsmentioning

confidence: 99%

“…A recent review deals specifically with point (ii) including some examples of flow systems ( Formenti et al., 2019 ). Other flow compatible reactions, such as Suzuki-Miyaura coupling on Pd catalysts, have been also reported; however, high loadings of Pd (up to 7 wt%) are necessary ( Yamada et al., 2020 ; Ichitsuka et al., 2019 ).…”

Section: Introductionmentioning

confidence: 99%

Nitro to amine reductions using aqueous flow catalysis under ambient conditions

2021

View full text Add to dashboard Cite

show abstract

“…Solid-materials (e. g., charcoal, alumina, silica, or polymer)supported Pd(0) nanoparticles (Pd NPs) have undergone extensive evaluation under continuous-flow conditions. [41][42][43][44][45][46][47][48][49][50] However, these catalysts are typically pretreated (or activated) through a procedure involving the calcination or reduction of Pd(II) precursors to Pd NPs, a process that may lead to undesired aggregation and leaching of Pd species. [35,40] In addition, several mechanistic studies indicated that when supported Pd NPs are employed as the catalyst, the oxidative addition of Pd(0) species with aryl halides tends to release Pd atoms from the surface of the catalyst to form soluble Pd(II) complexes, and these leached Pd species facilitate the reaction via a (quasi)homogeneous mechanism (Figure 1c).…”

Section: Introductionmentioning

confidence: 99%

“…Solid‐materials (e. g., charcoal, alumina, silica, or polymer)‐supported Pd(0) nanoparticles (Pd NPs) have undergone extensive evaluation under continuous‐flow conditions [41–50] . However, these catalysts are typically pretreated (or activated) through a procedure involving the calcination or reduction of Pd(II) precursors to Pd NPs, a process that may lead to undesired aggregation and leaching of Pd species [35,40] .…”

Section: Introductionmentioning

confidence: 99%

Recent Advancements in Continuous‐Flow Suzuki‐Miyaura Coupling Utilizing Immobilized Molecular Palladium Complexes

Zhang,

Yamada

2024

Chemistry A European J

View full text Add to dashboard Cite

Immobilized Pd‐catalyzed Suzuki–Miyaura coupling under continuous‐flow conditions using a packed‐bed reactor, representing an efficient, automated, practical, and safe technology compared to conventional batch‐type reactions. The core objective of this study is the development of an active and durable catalyst. In contrast to supported Pd nanoparticles, the attachment of Pd complexes onto solid supports through well‐defined coordination sites is considered a favorable approach for preparing highly dispersed and stabilized Pd species. These species can be directly employed in various flow reactions without the need for pre‐treatment. This concept paper explores recent achievements involving the application of immobilized Pd complexes as precatalysts for continuous‐flow Suzuki–Miyaura coupling. Our focus is to elucidate the significance of the designed catalyst structures in relation to their catalytic performance under flow conditions. Additionally, we highlight various reaction systems and catalyst packing methods, emphasizing their crucial roles in establishing a practical synthesis process.

show abstract

Continuous‐Flow Suzuki‐Miyaura Coupling in Water and Organic Solvents Promoted by Blends of Stabilized Convoluted Polymeric Palladium Catalysts and Polymeric Auxiliary Materials

Zhang

Ohno

Takaya

et al. 2023

Chemistry A European J

View full text Add to dashboard Cite

Given that heterogeneous palladium‐catalyzed C−C bond formation reactions under continuous‐flow conditions are well suited for the efficient and safe production of pharmaceuticals and functional materials, the development of active and durable catalysts for this purpose is a matter of high practical significance. Here, a previously established molecular convolution methodology was used to synthesize catalysts for Suzuki‐Miyaura coupling under flow conditions by blending convoluted polymeric palladium catalysts (prepared from copolymers of 4‐vinylpyridine and 4‐tert‐butylstyrene) and crosslinked polymeric auxiliary materials (prepared from copolymers of divinylbenzene and 4‐tert‐butylstyrene). The optimal catalyst exhibited high performance and durability and allowed numerous biaryl products such as liquid‐crystalline materials, organic electroluminescent materials, and pharmaceuticals to be continuously synthesized with turnover frequencies of up to 238 h−1. In a demonstration of practical utility, the developed catalytic system was used for the continuous synthesis of two pharmaceuticals (felbinac and fenbufen) in water as the sole solvent.

show abstract

Development of Facile and Simple Processes for the Heterogeneous Pd-Catalyzed Ligand-Free Continuous-Flow Suzuki–Miyaura Coupling

Cited by 6 publications

References 51 publications

Nitro to amine reductions using aqueous flow catalysis under ambient conditions

Nitro to amine reductions using aqueous flow catalysis under ambient conditions

Recent Advancements in Continuous‐Flow Suzuki‐Miyaura Coupling Utilizing Immobilized Molecular Palladium Complexes

Continuous‐Flow Suzuki‐Miyaura Coupling in Water and Organic Solvents Promoted by Blends of Stabilized Convoluted Polymeric Palladium Catalysts and Polymeric Auxiliary Materials

Contact Info

Product

Resources

About