Development of Polymeric Metal Catalysts via Molecular Convolution and of Catalytic Membrane-Installed Microflow Devices

Yamada, Yoichi M. A.; Uozumi, Yasuhiro

doi:10.5059/yukigoseikyokaishi.69.542

Cited by 9 publications

(3 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, Mizuno, Yus, Yamamoto, and Santoyo-Gonzaleza developed heterogeneous Cu catalysts for this reaction with TONs of 800, 198, 990, and 746, respectively, as the highest TONs . The development of heterogeneous immobilized polymeric metal catalysts with high efficiencies and reusabilities for this purpose still remains a major challenge.…”

Section: Resultsmentioning

confidence: 99%

Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

2012

Self Cite

View full text Add to dashboard Cite

Self-assembly of copper sulfate and a poly(imidazole-acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO(4) via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO(4) to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5-45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h(-1), respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

show abstract

Section: Resultsmentioning

confidence: 99%

Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…Metalloenzymes are supramolecular metal–organic hybrids of polypeptides and metal ions, which are essential proteins with vital activity to promote high-efficiency enzymatic reactions. , The high catalytic activity of metalloenzymes is attributable to (1) regulation of the molecular orientation between substrates, reactants, and the metalloenzyme; (2) cooperative catalysis of functional groups in the metalloenzyme; and (3) regulation of the reaction field in the metalloenzyme. To go even further and also ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, the development of polymer-supported metal catalysts is of particular interest. , …”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Poly(imidazole-palladium): Highly Active, Reusable Catalyst at Parts per Million to Parts per Billion Levels

2012

Self Cite

View full text Add to dashboard Cite

Metalloenzymes are essential proteins with vital activity that promote high-efficiency enzymatic reactions. To ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, it is important to develop metalloenzyme-inspired polymer-supported metal catalysts. Here, we present a highly active, reusable, self-assembled catalyst of poly(imidazole-acrylamide) and palladium species inspired by metalloenzymes and apply our convolution methodology to the preparation of polymeric metal catalysts. Thus, a metalloenzyme-inspired polymeric imidazole Pd catalyst (MEPI-Pd) was readily prepared by the coordinative convolution of (NH(4))(2)PdCl(4) and poly[(N-vinylimidazole)-co-(N-isopropylacrylamide)(5)] in a methanol-water solution at 80 °C for 30 min. SEM observation revealed that MEPI-Pd has a globular-aggregated, self-assembled structure. TEM observation and XPS and EDX analyses indicated that PdCl(2) and Pd(0) nanoparticles were uniformly dispersed in MEPI-Pd. MEPI-Pd was utilized for the allylic arylation/alkenylation/vinylation of allylic esters and carbonates with aryl/alkenylboronic acids, vinylboronic acid esters, and tetraaryl borates. Even 0.8-40 mol ppm Pd of MEPI-Pd efficiently promoted allylic arylation/alkenylation/vinylation in alcohol and/or water with a catalytic turnover number (TON) of 20,000-1,250,000. Furthermore, MEPI-Pd efficiently promoted the Suzuki-Miyaura reaction of a variety of inactivated aryl chlorides as well as aryl bromides and iodides in water with a TON of up to 3,570,000. MEPI-Pd was reused for the allylic arylation and Suzuki-Miyaura reaction of an aryl chloride without loss of catalytic activity.

show abstract

“…[1][2][3][4][5][6][7][8][9] I am interested in the nano/micro space-controlled reaction field that should provide novel functionality, including reactivity, stability and selectivity. For this purpose, I have developed three kinds of heterogeneous metal catalytic systems as follows: (1) Highly active polymeric base-metal complex catalysts.…”

Section: Introductionmentioning

confidence: 99%

Development of Batch and Flow Immobilized Catalytic Systems with High Catalytic Activity and Reusability

Yamada

2017

CHEMICAL & PHARMACEUTICAL BULLETIN

Self Cite

View full text Add to dashboard Cite

My mission in catalysis research is to develop highly active and reusable supported catalytic systems in terms of fundamental chemistry and industrial application. For this purpose, I developed three types of highly active and reusable supported catalytic systems. The first type involves polymeric base-supported metal catalysts: Novel polymeric imidazole-Pd and Cu complexes were developed that worked at the mol ppm level for a variety of organic transformations. The second involves catalytic membrane-installed microflow reactors: Membranous polymeric palladium and copper complex/nanoparticle catalysts were installed at the center of a microtube to produce novel catalytic membrane-immobilized flow microreactor devices. These catalytic devices mediated a variety of organic transformations to afford the corresponding products in high yield within 1-38 s. The third is a silicon nanowire array-immobilized palladium nanoparticle catalyst. This device promoted a variety of organic transformations as a heterogeneous catalyst. The Mizoroki-Heck reaction proceeded with 280 mol ppb (0.000028 mol%) of the catalyst, affording the corresponding products in high yield.

show abstract

Development of Polymeric Metal Catalysts via Molecular Convolution and of Catalytic Membrane-Installed Microflow Devices

Cited by 9 publications

References 63 publications

Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

Self-Assembled Poly(imidazole-palladium): Highly Active, Reusable Catalyst at Parts per Million to Parts per Billion Levels

Development of Batch and Flow Immobilized Catalytic Systems with High Catalytic Activity and Reusability

Contact Info

Product

Resources

About